Mathew Clingerman, Regional Engineering Manager, DuPont
Understanding The Advantages Of Having An Alkylation Unit In A Refinery Complex Presented By: Matthew L. Clingerman Regional Engineering Manager DuPont Clean Technologies For: Abu Dhabi International Downstream May 12th, 2015 Copyright © 2015. E. I. du Pont de Nemours and Company. All rights reserved. The DuPont Oval Logo, DuPontTM, The Miracles of ScienceTM and all products denoted with a ® or TM are trademarks or registered trademarks of E. I. du Pont de Nemours and Company or its affiliates. Fuel Specifications are Evolving Europe <10ppm (2009) USA <10ppm (2017) Russia <10ppm (2016) Japan China <10ppm (2018) <10ppm (2007) India <10ppm (2017) Thailand <50ppm (2012) Brazil <50ppm (2014) South Africa <10ppm (2017) Countries around the world are slowly adopting low-sulfur gasoline specifications 2 Copyright © 2015. E. I. du Pont de Nemours and Company. All rights reserved. The DuPont Oval Logo, DuPontTM, The Miracles of ScienceTM and all products denoted with a ® or TM are trademarks or registered trademarks of E. I. du Pont de Nemours and Company or its affiliates. Impact of Specifications • Strategies to reduce sulfur and regulated hydrocarbons also negatively impact octane • Octane loss can be recovered via different philosophies and available technologies: • • • Ethanol (primarily USA and Brazil) MTBE Alkylation 3 Copyright © 2015. E. I. du Pont de Nemours and Company. All rights reserved. The DuPont Oval Logo, DuPontTM, The Miracles of ScienceTM and all products denoted with a ® or TM are trademarks or registered trademarks of E. I. du Pont de Nemours and Company or its affiliates. MTBE • Olefins from the FCC are fed to the MTBE unit where isobutene is reacted with methanol to produce MTBE • • • • • Excellent RON/MON values Methanol is a very low cost feedstock Gradually phased-out in the USA, but still widely produced in other parts of the world Low olefin conversion(~29%) Methanol is required but at a lower cost to adding LPG to Gasoline 4 Copyright © 2015. E. I. du Pont de Nemours and Company. All rights reserved. The DuPont Oval Logo, DuPontTM, The Miracles of ScienceTM and all products denoted with a ® or TM are trademarks or registered trademarks of E. I. du Pont de Nemours and Company or its affiliates. Alkylation • • • • High yields and 100% conversion of olefins Excellent RON/MON/RVP Isobutane/LPG import typically not required, but some nC4 isomerization may be necessary. Alkylate is still maintaining high margins under current market conditions 5 Copyright © 2015. E. I. du Pont de Nemours and Company. All rights reserved. The DuPont Oval Logo, DuPontTM, The Miracles of ScienceTM and all products denoted with a ® or TM are trademarks or registered trademarks of E. I. du Pont de Nemours and Company or its affiliates. Global Shift in Gasoline Composition 6 Copyright © 2015. E. I. du Pont de Nemours and Company. All rights reserved. The DuPont Oval Logo, DuPontTM, The Miracles of ScienceTM and all products denoted with a ® or TM are trademarks or registered trademarks of E. I. du Pont de Nemours and Company or its affiliates. What is Alkylation? • The alkylation reaction combines isobutane with light olefins in the presence of a strong acid catalyst. The Resulting Product: Alkylate High Octane Low Vapor Pressure No Olefins No Aromatics Low Sulfur 7 Copyright © 2015. E. I. du Pont de Nemours and Company. All rights reserved. The DuPont Oval Logo, DuPontTM, The Miracles of ScienceTM and all products denoted with a ® or TM are trademarks or registered trademarks of E. I. du Pont de Nemours and Company or its affiliates. Alkylation Feedstock Olefins Makeup Isobutane • FCC • Purchased • MTBE Raffinate • Crude Unit • Coker • Saturated Gas Unit • Petrochemical • Butane Isomerization • Propylene / Amylene • Various Other Sources 8 Copyright © 2015. E. I. du Pont de Nemours and Company. All rights reserved. The DuPont Oval Logo, DuPontTM, The Miracles of ScienceTM and all products denoted with a ® or TM are trademarks or registered trademarks of E. I. du Pont de Nemours and Company or its affiliates. Alkylation Feedstock FCC Feed: ~25 mol% Isobutene (of total butenes) RON: 95-97 Volume Yield (true alkylate/olefin): ~1.78 Contaminants: Dienes • High FCC reaction temperatures • Product soluble in acid and hydrocarbon • Consumes acid and increases alkylate D86 End Point • Selective Hydrogenation Process (SHP / SHU) 9 Copyright © 2015. E. I. du Pont de Nemours and Company. All rights reserved. The DuPont Oval Logo, DuPontTM, The Miracles of ScienceTM and all products denoted with a ® or TM are trademarks or registered trademarks of E. I. du Pont de Nemours and Company or its affiliates. Alkylation Feedstock MTBE Raffinate: < 5 mol% iC4= (of total butenes) RON: Up to 98+ Volume Yield (true alkylate/olefin): ~1.78 Contaminants: Oxygenates • Poor operation of MTBE / TAME / ETBE Unit • Produce water & act as co-solvents • Oxygenate Removal Process: Absorber Column 10 Copyright © 2015. E. I. du Pont de Nemours and Company. All rights reserved. The DuPont Oval Logo, DuPontTM, The Miracles of ScienceTM and all products denoted with a ® or TM are trademarks or registered trademarks of E. I. du Pont de Nemours and Company or its affiliates. Alkylation vs. MTBE • • Process Yield Vol Prod/Vol Olefin Reacted RON Volume Per Volume of Olefin Reacted MON Volume Per Volume of Olefin Reacted MTBE 1.25 144 121 Alkylation C4= 1.78 170 165 MTBE has very high octane (~120), but low olefin conversion Alkylation may provide greater improvement in gross margin versus and MTBE unit 11 Copyright © 2015. E. I. du Pont de Nemours and Company. All rights reserved. The DuPont Oval Logo, DuPontTM, The Miracles of ScienceTM and all products denoted with a ® or TM are trademarks or registered trademarks of E. I. du Pont de Nemours and Company or its affiliates. STRATCO® Alkylation Technology RECYCLE ISOBUTANE PROPANE PRODUCT REFRIGERATION ACID EFFLUENT TREATING FEED PREPARATION SPENT ACID OLEFIN FEED MAKEUP ISOBUTANE SPENT WATER ALKYLATION REACTION FRESH ACID F R A C T I O N A T I O N PROCESS WATER n-BUTANE PRODUCT MAKEUP ISOBUTANE ALKYLATE PRODUCT BLOWDOWN REFINERY WASTEWATER TREATMENT SPENT ACID Copyright © 2015. E. I. du Pont de Nemours and Company. All rights reserved. The DuPont Oval Logo, DuPontTM, The Miracles of ScienceTM and all products denoted with a ® or TM are trademarks or registered trademarks of E. I. du Pont de Nemours and Company or its affiliates. 12 Reaction Zone Configuration Acid Settler Spent Acid Fresh Acid TI TI Refrigerant Recycle Reactor Effluent Combined Feed M Contactor™ Reactor PC 13 Copyright © 2015. E. I. du Pont de Nemours and Company. All rights reserved. The DuPont Oval Logo, DuPontTM, The Miracles of ScienceTM and all products denoted with a ® or TM are trademarks or registered trademarks of E. I. du Pont de Nemours and Company or its affiliates. STRATCO® Contactor™ Reactor Reactor Effluent Out Emulsion to Acid Settler Circulation Tube Tube Bundle Assembly Emulsion Recycle Hydrocarbon Impeller Motor Reactor Effluent In Hydraulic Head Contactor™ Reactor Shell Three sizes available: • Model 42 • Model 63 • Model 74 14 Copyright © 2015. E. I. du Pont de Nemours and Company. All rights reserved. The DuPont Oval Logo, DuPontTM, The Miracles of ScienceTM and all products denoted with a ® or TM are trademarks or registered trademarks of E. I. du Pont de Nemours and Company or its affiliates. STRATCO® Contactor™ Reactor 15 Copyright © 2015. E. I. du Pont de Nemours and Company. All rights reserved. The DuPont Oval Logo, DuPontTM, The Miracles of ScienceTM and all products denoted with a ® or TM are trademarks or registered trademarks of E. I. du Pont de Nemours and Company or its affiliates. STRATCO® Contactor™ Reactor 16 Copyright © 2015. E. I. du Pont de Nemours and Company. All rights reserved. The DuPont Oval Logo, DuPontTM, The Miracles of ScienceTM and all products denoted with a ® or TM are trademarks or registered trademarks of E. I. du Pont de Nemours and Company or its affiliates. STRATCO® Reaction Section Low Strength High Strength Acid Settler Acid Settler FC FC Fresh Acid 99.2 wt% M AI Acid Settler FC Intermediate ~ 95 wt% AI AI Spent Acid ~ 90 wt% Intermediate ~ 92-93 wt% Contactor™ Reactor M Contactor™ Reactor M Contactor™ Reactor Refrigerant Recycle Olefin And Isobutane Olefin And Isobutane Olefin And Isobutane 17 Copyright © 2015. E. I. du Pont de Nemours and Company. All rights reserved. The DuPont Oval Logo, DuPontTM, The Miracles of ScienceTM and all products denoted with a ® or TM are trademarks or registered trademarks of E. I. du Pont de Nemours and Company or its affiliates. Segregated STRATCO® Reaction Section Low Strength High Strength Acid Settler Acid Settler FC FC Fresh Acid 99.2 wt% M AI Acid Settler FC Intermediate ~ 94 wt% AI AI Spent Acid ~ 87 wt% Intermediate ~ 91 wt% Contactor™ Reactor M Contactor™ Reactor M Contactor™ Reactor Refrigerant Recycle C3 Olefin And Isobutane C4 Olefin And Isobutane C5 Olefin And Isobutane 18 Copyright © 2015. E. I. du Pont de Nemours and Company. All rights reserved. The DuPont Oval Logo, DuPontTM, The Miracles of ScienceTM and all products denoted with a ® or TM are trademarks or registered trademarks of E. I. du Pont de Nemours and Company or its affiliates. STRATCO® Alkylation Technology Sustained Performance • Unit startup in 2009 – MTBE Raffinate Feed • Successful performance test within two weeks of initial startup • Sustained performance • Alkylate data from 2014 • RON 98.2 • End Point 190C • Sulfur 1 wt ppm • Only a one day unplanned shutdown 19 Copyright © 2015. E. I. du Pont de Nemours and Company. All rights reserved. The DuPont Oval Logo, DuPontTM, The Miracles of ScienceTM and all products denoted with a ® or TM are trademarks or registered trademarks of E. I. du Pont de Nemours and Company or its affiliates. Licensor Qualifications STRATCO® Alkylation Technology Global Leader in Sulfuric Acid Alkylation Technology Total Licenses – 94 Repeat Customers – 47 STRATCO®/MECS® Complexes - 34 MECS® Spent Acid Regeneration Technology Global Leader in Sulfuric Acid Technologies Total SAR Licenses - 60 Largest Alkylation, Metallurgical and Chemical SAR Acid Plants Over 1,000 Customers Worldwide 20 Copyright © 2015. E. I. du Pont de Nemours and Company. All rights reserved. The DuPont Oval Logo, DuPontTM, The Miracles of ScienceTM and all products denoted with a ® or TM are trademarks or registered trademarks of E. I. du Pont de Nemours and Company or its affiliates. Summary • Proven, flexible technology for upgrading olefins from an FCC or MTBE unit • High value product • Alkylate is an excellent blend stock for meeting lowsulfur gasoline specifications 21 Copyright © 2015. E. I. du Pont de Nemours and Company. All rights reserved. The DuPont Oval Logo, DuPontTM, The Miracles of ScienceTM and all products denoted with a ® or TM are trademarks or registered trademarks of E. I. du Pont de Nemours and Company or its affiliates. Thank You Copyright © 2015. E. I. du Pont de Nemours and Company. All rights reserved. The DuPont Oval Logo, DuPontTM, The Miracles of ScienceTM and all products denoted with a ® or TM are trademarks or registered trademarks of E. I. du Pont de Nemours and Company or its affiliates.
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