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Gasoline Benzene Reduction

Through Reformate Alkylation


Catalytic Technology

Dr. El-Mekki El-Malki


ExxonMobil Research & Engineering
Company (EMRE)

Ronald Birkhoff
Badger Licensing LLC AIChE Regional Process Technology
Conference
October 7th - 8th 2010
Galveston, TX

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Research and Engineering Licensing LLC
Reducing Benzene in Gasoline Pool

1 vol %
Europe
1 vol %
1-5 vol %
range
0.62 vol % ASIA

1.5-4 vol %
Americas
range
Middle East
1-2.5 vol % Africa
range 1 vol %
Australia &
Pacific

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Licensing LLC
Typical Gasoline Pool Benzene in US

Average Typical
Volume in Benzene Benzene
Components Gasoline % Level % Contribution %

Reformate ~ 30 3-11 ~ 75

FCC Gasoline ~ 36 0.5-2 ~ 16

Hydrocrackate ~3 1-5 ~3

Others ~ 31 0-3 ~6
Reference: EPA-HQ-OAR-2005-0036; FRL-8041-2, Table VII.F-2

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Licensing LLC
Refiner’s Options

Octane
Gasoline Gasoline Hydrogen Light
Volume Pool Balance Olefin
Reformer Feed Reduced
Tailoring Production

No
Benzene Extraction change

High
Benzene Saturation consumption

No Upgrade
BenzOUT™ consumption to Mogas

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Licensing LLC
BenzOUT™ Process Configuration

Benzene Light Olefins


Concentrate Pretreatment

Light end

Full Reformate Splitter BenzOUT


Reactor
Splitter

Products

¾ Fixed Bed Reactor Configuration


ƒ Adiabatic or Isothermal
ƒ Carbon steel equipment and no compressor needed
¾ Process Uses a Proprietary Catalyst
ƒ High activity, high selectivity

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Licensing LLC
BenzOUT™ – Reducing Benzene while
Boosting Product Value

¾ BenzOUT Process Alkylates Benzene-Containing Streams with


Light Olefins to Produce Alkyl Aromatics for Gasoline Blending

¾ Incentives Include:
ƒ Reduced Benzene to meet regulations

ƒ Upgrading of Light Olefins to high octane gasoline

ƒ Increased Gasoline volume and reducing RVP

ƒ Avoidance of hydrogen consumption

ƒ Retained Reformer flexibility e.g. hydrogen and octane production

¾ Commercially demonstrated

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Licensing LLC
Benzene Conversion Can Be Achieved
According to Need

100

Benzene Conversion (%)

0
Olefin/Aromatic Ratio

¾ Primary Reaction Chemistry is Alkylation of Benzene with Olefin


ƒ Benzene conversion controlled by Olefin/Aromatic ratio

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Licensing LLC
Example of BenzOUT Boosting
Product Volume

Benzene Light Olefins


Concentrate Pretreatment

Light end

40 KB/D Splitter BenzOUT


Full Reformate Reactor
Splitter

42.3
KB/D
¾ Approx. 5% Volume Increase Based on Full Reformate

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Licensing LLC
Example of BenzOUT™ Product
Properties

Typical Gasoline End Point


Temperature (oF)

Product
Feed

% Evaporated
¾ Final Product Properties are a Function of Feed Composition and
Benzene Conversion
ƒ Approx. (R+M)/2 increase of 2-5
ƒ Approx. RVP reduction of 0.5 PSI

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Licensing LLC
Process Demonstrated in a
North American Refinery
Light Olefin
Reformate

BenzOUT
Catalyst

Mogas Blending

¾ BenzOUT Catalyst Drop-in Application


ƒ Only minor modification to the Polygas Unit
¾ BenzOUT Demonstration Conducted in One of the 3 Tubular Reactors
¾ BenzOUT and Polygas Products Combined for Mogas Blending

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Licensing LLC
Commercial Trial Results Confirmed
Pilot Plant Results
100
Benzene Conversion (%)

Olefin/Aromatic ratio
0
0 10 20 Days on
30 Stream 40 50 60

¾ High Benzene Conversion Demonstrated


¾ Commercial Results Confirm Pilot Plant Data

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Licensing LLC
BenzOUT™ Technology Delivery

¾ ExxonMobil Research & Engineering Company (EMRE) and


Badger Licensing LLC formed an alliance to license BenzOUT
Technology
ƒ BenzOUT offered exclusively by Badger Licensing LLC

ƒ Badger will be the contracting party responsible for the process


license, proposals and basic design packages.

ƒ EMRE will supply the BenzOUT Catalyst

¾ ExxonMobil and Badger have a continuing 30 year history of


licensing petrochemical processes

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Licensing LLC
BenzOUT™ Advantages - Summary

¾ Benzene achieves low Benzene content in the gasoline pool


AND:
ƒ Upgrades light olefins to high octane gasoline blendstock

ƒ Increases reformate volume and octane value

ƒ Eliminates impact on hydrogen balance

¾ Simple and reliable process

¾ Flexible process design – simple retrofit or grassroots tie-in

¾ Commercially demonstrated

¾ Available for license through Badger-EMRE Alliance

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Licensing LLC
THANK YOU

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Licensing LLC