On Purpose Alkylation for Meeting Gasoline Demand

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1 On Purpose Alkylation for Meeting Gasoline Demand Matthew Clingerman MERTC Annual Meeting, Bahrain 23 rd 24 th January 2017 DuPont Clean Technologies Copyright 2017 E. I. du Pont de Nemours and Company. All rights reserved. The DuPont Oval Logo, DuPont and all products denoted with a or are registered trademarks or trademarks of DuPont or its affiliates.

2 Agenda Introduction to DuPont Clean Technologies Market Overview & Challenges On Purpose Alkylation STRATCO Alkylation Technology Summary 2

3 Our Purpose Through science and engineering, we solve some of the world s greatest challenges. DuPont has been bringing world class science and engineering to the global marketplace in the form of innovative products, materials, and services since National Geographic Image 3

4 DuPont Clean Technologies IsoTherming Hydroprocessing Technology STRATCO Alkylation Technology MECS Sulfuric Acid Technology BELCO & DynaWave Scrubbing Technologies Unique technology for removal of sulfur to ultralow levels from diesel & intermediate petroleum products Leading technology for the production of low sulfur, high octane gasoline blend stock Leading technology for the production of sulfuric acid and related high performance products Leading technologies for air emissions reduction in FCCs & SRUs for SOx, NOx, and particulates DOWNSTREAM OIL & GAS MIDSTREAM OIL & GAS PETROCHEMICAL FERTILIZER, METALS, CHEMICALS MARINE 4

5 Clean Technologies Portfolio Drivers <10 ppm ppm ppm ppm ppm ppm No Information Developing Region / Higher Demand Gasoline Sulfur Limits in 2020; Global Fuel Quality Developments, Stratas Advisors, 11th Global Partners Meeting of the Partnership for Clean Fuels and Vehicles (PCFV), 6 7 June 2016, London, UK. 5

6 Alkylation Market Drivers Coupled with increasing gasoline demand, increasingly stringent specifications are not just for sulfur; RON, Rvp, Olefins, etc. are also regulated More efficient engines (high compression & direct injected) prefer higher octane gasoline Shale oil production yields lots of LPG (propane & butane) World Oil Outlook 2015, Organization of Petroleum Exporting Countries, Vienna, Austria, Oct

7 Modern Fuel Specifications Euro V US Tier 3 China 5 Research Octane Number (min) BS VI Vapor pressure (summer), kpa Olefins, vol% Aromatics, vol% Benzene, vol% Sulfur content, ppm Automotive manufacturers are producing higher efficiency engines that require high octane fuels Regulations to reduce RVP, sulfur, aromatics, benzene all negatively impact octane Countries around the world are slowly adopting similar lowsulfur gasoline specifications 7

8 Alkylation Market Drivers Octane loss can be recovered via different philosophies and available technologies: Ethanol: Increases RVP by 7 8 kpa MTBE/ETBE: Banned in US/C, legislation favoring ETBE Reformate: Increases aromatics Dimerate: Highly olefinic and low yield per volume olefin Alkylate 8

9 Alkylation Market Drivers In the current market environment, individual gasoline components have taken on new roles with respect to blending strategies and economics. Fuel blends globally are following similar trends as legislation is introduced Average Alkylate Content in Gasoline Pool Volume %

10 Global Gasoline Composition Shift Historically, the international demand for alkylate has lagged behind that of the U.S. due to economic and environmental factors Increasing consumption and heightened global environmental awareness, the importance of alkylate as a gasoline blend component is rapidly increasing worldwide As a result, global alkylation capacity is approximately 2,000,000 BPSD (78,500 kmta) 10

11 What is Alkylate? Butene IsoButane 2,2,4 Trimethylpentane Alkylate is formed by reacting isobutane with light olefins (C 3=, C 4=, C 5= ) in the presence of a strong acid catalyst. High Octane Low Vapor Pressure No Olefins No Aromatics Low Sulfur 11

12 Alkylation Feed & Product Olefins Alkylate Quality FCC Olefins MTBE Raffinate FCC MTBE Raffinate Coker Propylene / Amylene Makeup Isobutane Crude Unit Saturated Gas Unit Butane Isomerization Purchased / Other Research Octane Number Vapor pressure, kpa Olefins, vol% 0 0 Aromatics, vol% 0 0 Benzene, vol% 0 0 Sulfur content, ppm 5 (max) 5 (max) 12

13 On Purpose Alkylation Shale Oil Boom has led to higher natural gas liquid (NGL) compositions Increase in isobutane and normal butane Few outlets for normal butane = falling costs Butanes sold at large discount nc 4 isomerization to ic 4 dehydrogenation to ic 4 = Increased propane composition Propane dropped to negative cost or being sold at shipping costs 13

14 On Purpose Alkylation Propane, normal butane and isobutane can be dehydrogenated, reacted to produce high value alkylate Propane Normal Butane Butane Isomerization Isobutane Dehydrogenation Propylene Isobutylene STRATCO Alkylation Alkylate MECS SAR 14

15 Alkylation Options Hydrofluoric Acid High quality alkylate, low cost to regenerate catalyst Higher maintenance costs Very unsafe; catastrophic consequence in the event of an HF release Ionic Liquid Alkylation Very high capital cost High utility consumption Lower product quality Unproven at large capacities Solid Catalyst High cost of catalyst with uncertain life cycle Lower product quality by 1 2 RON Reactors frequently in regeneration mode Unproven at large capacities Sulfuric Acid Alkylation Highest product quality Safe handling is well known and practiced STRATCO technology has the largest percentage of installed capacity 15

16 STRATCO Alkylation Technology 5 6 Years in Alkylation No. of Licensed Units > 90 Licenses in last 10 years 30 Installed Capacity, bbls 984,500 16

17 STRATCO Alkylation Technology 17

18 STRATCO Reaction Section 18

19 Advantages of STRATCO Technology Feed Flexibility Segregation and processing of C3, C4, and C5 olefins without additional units upstream Alkylation of non traditional feedstocks Optimized Reaction Zone Proven best in class product quality. Colder temperatures require additional utilities and provide no product quality improvement. Proven Record of Reliability Units built in 1940s are still in operation. US Alkylation units consistently make 4 5 year T/A plan. Unit successfully restarted after being shut down for 20 years. 19

20 STRATCO On Purpose Alkylation Isobutylene Test Run Test Run Conditions Purchased Olefin Feed Reactor Temperature Isobutane to Olefin Ratio (I/O) Fresh Acid Strength Average Acid Strength 99+% ic4= 7.2 C 12:1 (molar) 99.2 wt% 93 wt% Test run performed in a commercial STRATCO alkylation unit. Olefin Space Velocity (OSV) 0.5 hr 1 Test Run Duration 52 hours 20

21 STRATCO On Purpose Alkylation Isobutylene Test Run Results FBP C D 86 FBP Test Run Results Alkylate D 86 FBP decreased throughout the test run as the unit stabilized and process conditions were optimized. Actual results at the end of the test run closely match the DuPont pilot plant FBP of 216 C. 21

22 STRATCO On Purpose Alkylation Isobutylene Test Run Results 96.0 RON Test Run Results Alkylate RON also improved throughout the test run. Actual results at the end of the test run exceed the DuPont pilot plant RON of RON

23 STRATCO On Purpose Alkylation Typical Product Quality Butylene 1 Butene 2 Butene 100% Isobutylene MTBE Raffinate FCC Butylenes True Alkylate RON True Alkylate R+M/ True Alkylate D 86 FBP ( C) Reaction Acid Consumption (kg acid / metric ton whole alkylate)

24 STRATCO On Purpose Alkylation Typical Product Quality Other Olefins Various Butylenes 100% Propylene 100% Amylene True Alkylate RON True Alkylate R+M/ True Alkylate D 86 FBP ( C) <220 <220 Reaction Acid Consumption (kg acid / metric ton whole alkylate)

25 STRATCO Alkylation Technology Summary Alkylate, with its superior blending properties, continues to be a key and desirable component for clean gasoline DuPont is the preferred licensor for Alkylation & Spent Acid Regeneration technologies, with over 90 licenses worldwide STRATCO Alkylation produces the highest quality alkylate in a flexible & highly reliable process 25

26 Copyright 2017 E. I. du Pont de Nemours and Company. All rights reserved. The DuPont Oval Logo, DuPont and all products denoted with a or are registered trademarks or trademarks of DuPont or its affiliates.

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