SCANFINING™ TECHNOLOGY: A PROVEN OPTION FOR

PRODUCING ULTRA-LOW SULFUR CLEAN GASOLINE

Mohan Kalyanaraman
Sean Smyth
John Greeley
Monica Pena

LARTC 3rd Annual Meeting

9-10 April 2014
Cancun , Mexico
 Agenda

►Drivers of Ultra-Low Sulfur Clean Gasoline

►Sulfur Challenge in Mogas pool
►Using Chemistry of Sulfur Molecules
►Configuration Alternatives
− SCANfining™ I Process
− SCANfining II Process
− ZEROMERTM Process
►SCANfining Catalyst
►Summary

◄2►
Regulatory Concerns Have Forced Lower S in Gasoline

► Removal of sulfur improves catalytic converter performance & reduces

emissions
► Sulfur Reduction increasingly mandated in countries around the world
► US EPA has proposed rule to lower gasoline S to 10 ppm as part of Tier 3
► Refiners are looking to future proof their investment

◄3►
 Gasoline Pool and Sulfur Removal Challenge

Reformate Hi Octane, Low S

Straight Run
Low Octane, Moderate S

Alkylate Hi Octane, Low S

FCC naphtha Hi Octane, Hi S

►FCC Naphtha is a major component of Mogas pool

 Challenge is to maintain the high Octane Olefins & remove the Sulfur

◄4►
Options to Lower S in Gasoline in Current Refineries
►Increased severity in FCC pre-treat
 Increased H2 consumption, decreased catalyst cycle length

►Use of Gasoline Sulfur Reduction additives in FCC

 Additional cost, low sulfur removal

►Post treatment of FCC Naphtha

 Required for ULS Gasoline
 For refiners with existing post treatment, increased severity may be required

►Investment to augment/ revamp existing post treating units can be

profitable in a high Octane value environment

◄5►
 Molecular Understanding of FCC Naphtha

300

250
S (wppm)

200 Mercaptan
sulfur
Non
150 mercaptan
sulfur
100

50

0
0 20 40 60 80
wt%

► Olefins are distributed unevenly with Light Cat Naphtha having more olefins
► Intermediate Cat Naphtha, Heavy Cat Naphtha have lower Olefins but higher amount of
Sulfur
► Mercaptan Sulfur is higher in the front end of FCC Naphtha

◄6►
 Processing Schemes for FCC Naphtha

UNIT

► Design option based on Feed & Product Sulfur target, refiners preference, constraints
► For Ultra Low Sulfur Gasoline from high Sulfur streams, a combination of approaches
may be required
► Revamps using change of catalyst, some post modification may be cost effective

◄7►
SCANfining Process: Selective Cat Naphtha Hydrofining
provides the highest value at lowest Capex
►SCANfining process utilizes proprietary catalyst and conditions targeted to:
 Maximize desulfurization to meet S specification below 10 ppmw
 Minimize olefin saturation/Octane loss
 Minimize mercaptan recombination

►Fixed bed hydroprocessing with variety of configurations allow processing feedstocks

with wide or narrow boiling range, high or low sulfur content
 Relatively small, low pressure reactors
 Conventional hydrotreating temperatures
 EMRE proprietary catalyst
 EMRE proprietary reactor internals extend cycle length
 Low hydrogen consumption
 No hydrocracking reactions that lead to RVP increase
 Retrofit easily into spare equipment such as semi-regen reformer, kerosene hydrotreater or
naphtha hydrotreater

◄8►
 Large Base of Installed SCANfining Process Applications

► 43 ExxonMobil or Licensed SCANfining Units worldwide

 Over 1.3 Million BD Capacity
 SCANfining I and SCANfining II, many making 10 ppm S
 SCANfining I with Zeromer
Cumulative SCANfining Unit Capacity, KBD

1400

1200

ExxonMobil
1000
Licensee
800

600

400

200

0
2H02 & 1H03 2H03 1H04 2H04 Current
Earlier

◄9►
 Sulfur Removal Chemistry

Mercaptans
Caustic Treat R-S-S-R
R-SH Hydrotreat
R-H + H 2S
Thiophenes
Hydrotreat
R-H + H 2S
R
S Octane
Loss
Olefins
Hydrotreat
R=R ' R-R '

Reversion Recombinant
H-S-H + R=R R-SH
Mercaptans

◄ 10 ►
Evolution of SCANfining Process: SCANfining I

SCANfining I

► HDS Range：Feed S ~1500 to ~Product S 30 wppm

► Relatively low capital investment, retrofit capability
► For lower S feeds, 10 ppm S achievable; For higher S feeds, need additional
treatments (e.g., mercaptan removal)

◄ 11 ►
Mercaptans Limit SCANfining Process Selectivity
SCANfining I Processing Full Range Cat Naphtha: Low S, High Olefins
140
Total Sulfur
120 Non-Mercaptan Sulfur
wppm Sulfur

100

80 Mercaptan Sulfur
60

40

20

0
0 10 20 30 40 50 60 70
% Olefin Saturation

► Better olefin retention leads to higher mercaptan contribution to total S

► Reversion mercaptan levels governed by process conditions
► Alternative process designs control mercaptans content in product based on
development of mercaptan reversion kinetics

◄ 12 ►
Preferred Regions for SCANfining Process Options

Technology Selection Depends on Feed Sulfur and Bromine Number

For Ultra-Low Product Sulfur Targets

ZEROMER Process SF-II break-even

ZEROMER Process SF-I break-even
Feed Sulfur, ppm

SF-II

ZEROMER
Increasing

(SF-1 with Mercaptan Conversion

Preferred)

SF-I Preferred

Increasing Feed Bromine Number

◄ 13 ►
 Ultra-low Sulfur by Mercaptan Removal with
Incremental Investment
Add-Ons for
Ultra-Low Sulfur

SCANfining II
Process
FCC Naphtha SCANfining I
Process
(Full Range or
Fractionated) (For Near-Term
Sulphur Needs)
ZEROMER Process
Catalytic
►Smallincrease in capital vs. 1-Stage unit Destruction
►+10-15% increase for ZEROMER Process of Mercaptans
►+20-25% increase for SCANFining II Process

◄ 14 ►
Robustness of Catalyst - 2-Stage Unit with High Feed
Sulfur making 10 ppm Product Sulfur

► European 2-stage unit with high Feed Sulfur and 10 ppm product Sulfur
► Catalyst on stream for many years

◄ 15 ►
 EMRE has Developed Newer SCANfining Catalysts

► Proprietary RT-225TM: proven

 Designed specifically for selective HDS of FCC
naphtha
 Minimizes olefin saturation / octane loss
 Reliable, high selectivity, good activity
maintenance RT-225 Catalyst
 Octane loss stays the same or improves as
catalyst ages
► Proprietary RT-235TM: proven
 Designed for selective HDS of FCC naphtha
 Higher Selectivity
 Higher activity
 Proven, Reliable in multiple units
 Robust, CO tolerant RT-235 Catalyst

◄ 16 ►
 RT-235 Octane Savings in Commercial Applications
Match Pilot Runs

►Side byside tests of RT- 20

225 and RT-235 on light
cat naphtha

Olefin Saturation (%)

15
RT-225

►Engine tests on products 10

showed expected octane
savings 5
RT-235

►Average of 25% Octane 0

savings 75 80 85 90 95 100
HDS (%)

17 ◄ 17 ►
 Summary
► Reducing Sulfur levels in Mogas requires a variety of approaches

► Understanding the Chemistry of FCC Naphthas is critical to designing post

treat systems

► EMRE has wide experience base with variety of feeds and designing for
high to low feed Sulfur
• 43 ExxonMobil or Licensed SCANfining Units worldwide
• Over 1.3 Million BD Capacity

► EMRE has continued research into refinement of process / catalyst

configuration
• New generation of SCANfining catalyst further improves selectivity

► Proven cost effective approach to provide robust solution

◄ 18 ►
Questions