On Purpose Alkylation for Meeting Gasoline Demand · • As a result, global alkylation capacity is approximately 2,000,000 BPSD (78,500

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.

DuPont Clean Technologieswww.cleantechnologies.dupont.com

Matthew Clingerman

MERTC Annual Meeting, Bahrain

23rd – 24th January 2017

On‐Purpose Alkylation for Meeting Gasoline Demand

2Copyright © 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.

Agenda

Introduction to DuPont Clean Technologies

Market Overview & Challenges

On‐Purpose Alkylation

STRATCO® Alkylation Technology

1

2

3

4

Summary5

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. 3

Our PurposeOur 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 1802.

© National Geographic Image


DuPont Clean TechnologiesIsoTherming®

Hydroprocessing Technology

STRATCO®

Alkylation TechnologyMECS® Sulfuric Acid Technology

BELCO® & DynaWave® Scrubbing Technologies

Unique technology for removal of sulfur to ultra‐low 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

FERTILIZER, METALS, CHEMICALS MARINEPETROCHEMICALMIDSTREAM OIL & GAS


Clean Technologies Portfolio Drivers

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.

<10 ppm

11 – 30 ppm

31 – 50 ppm

51 – 150 ppm

151 – 500 ppm

501 – 2500 ppm

No Information

Developing Region / Higher Demand


• 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)

Alkylation Market Drivers

World Oil Outlook 2015, Organization of Petroleum Exporting Countries , Vienna, Austria, Oct. 2015.


Modern Fuel Specifications

Euro‐V US Tier 3 China 5 BS‐VI

Research Octane Number (min) 95 93 95 91

Vapor pressure (summer), kPa 60.0 48.0 65.0 60.0

Olefins, vol% 18.0 10.0 24.0 21.0

Aromatics, vol% 35.0 25.0 40.0 35.0

Benzene, vol% 1.0 0.62 1.0 1.0

Sulfur content, ppm 10 10 10 10

• 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 low‐sulfur gasoline specifications



• 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



• 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

0

3

6

9

12

15

Volume %

Average Alkylate Content in Gasoline Pool


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)


What is Alkylate?

Alkylate is formed by reacting isobutanewith light olefins (C3=, C4=, C5=) in the presence of a strong acid catalyst.

• High Octane• Low Vapor Pressure• No Olefins• No Aromatics• Low Sulfur

Butene IsoButane 2,2,4 Trimethylpentane


Alkylation Feed & Product

Makeup IsobutaneMakeup Isobutane

• Crude Unit• Saturated Gas Unit• Butane Isomerization• Purchased / Other

• Crude Unit• Saturated Gas Unit• Butane Isomerization• Purchased / Other

• FCC• MTBE Raffinate• Coker• Propylene / Amylene

• FCC• MTBE Raffinate• Coker• Propylene / Amylene

OlefinsOlefins

Research Octane Number 95‐97 98+

Vapor pressure, kPa 35.0 35.0

Olefins, vol% 0 0

Aromatics, vol% 0 0

Benzene, vol% 0 0

Sulfur content, ppm 5 (max) 5 (max)

Alkylate Quality FCC Olefins

MTBE Raffinate



• 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• nC4 isomerization to iC4 dehydrogenation to iC4=

• Increased propane composition• Propane dropped to negative cost or being sold at shipping costs



• Propane, normal butane and isobutane can be dehydrogenated, reacted to produce high value alkylate

Butane Isomerization

STRATCO®Alkylation

Dehydro‐genation

NormalButane

Isobutane

Propane

PropyleneAlkylate

Isobutylene

MECS®SAR

MECS®SAR


Sulfuric Acid Alkylation• Highest product quality• Safe handling is well known and practiced• STRATCO® technology has the largest

percentage of installed capacity

Hydrofluoric Acid• High quality alkylate, low cost to regenerate

catalyst• Higher maintenance costs• Very unsafe; catastrophic consequence in

the event of an HF release

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

Alkylation Options

Ionic Liquid Alkylation• Very high capital cost• High utility consumption• Lower product quality• Unproven at large capacities



Years in Alkylation 75+

No. of Licensed Units > 90

Licenses in last 10 years 30

Installed Capacity, bbls 984,500

44

5

3

6

95 8

2




STRATCO® Reaction Section


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.


STRATCO® On‐Purpose AlkylationIsobutylene Test Run

Test Run Conditions

Purchased Olefin Feed 99+% iC4=

Reactor Temperature 7.2°C

Isobutane to Olefin Ratio (I/O) 12:1 (molar)

Fresh Acid Strength 99.2 wt%

Average Acid Strength 93 wt%

Olefin Space Velocity (OSV) 0.5 hr ‐1

Test Run Duration 52 hours

Test run performed in a commercial STRATCO®

alkylation unit.


205

210

215

220

225

230

235

240

FBP °C

D‐86 FBP Test Run Results

STRATCO® On‐Purpose AlkylationIsobutylene 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.


STRATCO® On‐Purpose AlkylationIsobutylene 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 95.0.

94.0

94.5

95.0

95.5

96.0

RON

RON Test Run Results


STRATCO® On‐Purpose AlkylationTypical Product Quality ‐ Butylene

1‐Butene 2‐Butene 100% Isobutylene

MTBERaffinate

FCC Butylenes

True Alkylate RON 98 ‐ 99 98 ‐ 99 95 ‐ 96 98 ‐ 99 96 ‐ 97

True Alkylate R+M/2 96 ‐ 97 96 ‐ 97 93 ‐ 94 96 ‐ 97 94 ‐ 96

True Alkylate D‐86 FBP (°C) 150 ‐ 175 150 ‐ 175 205 ‐ 220 165 ‐ 190 175 ‐ 205

Reaction Acid Consumption (kg acid / metric ton whole alkylate)

51 ‐ 59 51 ‐ 59 43 ‐ 51 51 ‐ 59 51 ‐ 59


STRATCO® On‐Purpose AlkylationTypical Product Quality – Other Olefins

Various Butylenes

100%Propylene

100% Amylene

True Alkylate RON 96 ‐ 99 89 ‐ 91 87 ‐ 91

True Alkylate R+M/2 93 ‐ 97 88 ‐ 91 87 ‐ 90

True Alkylate D‐86 FBP (°C) 150 ‐ 220 <220 <220

Reaction Acid Consumption (kg acid / metric ton whole alkylate) 51 ‐ 59 68 – 170 68 ‐ 135


STRATCO® Alkylation TechnologySummary

• 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

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.

Documents

On Purpose Alkylation for Meeting Gasoline Demand · • As a result, global alkylation capacity is approximately 2,000,000 BPSD (78,500