Exploring Gasoline Sulfur Reduction

Opportunities
Agenda

FCC Feed Sulfur Distribution

FCC Gasoline Sulfur Species
FCC Operating Variables Influencing Gasoline Sulfur
Grace GSR Technologies
Commercial Applications

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Introduction
Problem:
When gasoline is burned:
Sulfur in gasoline is oxidized to SO2
SO2 inhibits the performance of automotive emissions control devices which
control CO and NOx

Globally, government environmental agencies are limiting sulfur in

gasoline
Leading industrialized countries imposing a 10 ppm limit

Solution:
Gasoline sulfur reduction catalyst and additive solutions offer
refineries:
Lower gasoline sulfur
Improved gasoline properties including RON
When gasoline post-treater severity is reduced
Decreased
Click to edit text FCC
styles feed-pretreater operating cost
Cost effective alternative to hardware
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Global Gasoline Sulfur Limits

Recently updated to 10 ppm

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Gasoline Sulfur Global Limits

2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016 2017 2018

Japan > 50 10

Hong Kong > 10

EU-27 50 10

South Korea > 10

Taiwan > 10

Russia 500 150 50 10

South Africa 1000 500 10

U.S. 30/90 30/80 10/80

/300

China* > 500 150 50 10

Chile > 15

Canada 30/80

Australia 150 50

NZ > 50

Thailand 150 50

Brazil* > 1000 50

Malaysia > 500 50

India* > 500 150

Indonesia > 500 150

Ecuador > 650

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US Tier 3 - Gasoline Sulfur Limit

Impacts Vehicle Emissions and Fuels Quality Standards

Reduction of average gasoline sulfur level to 10 ppm by January 2017
Gasoline sulfur cap at the refinery gate 80 ppm
Averaging, Banking and Trading program (ABT) Credit Program
Credits can carry over from Tier 2
Tier 3 Credits can be accumulated until January 2017
Credits might extend full Tier 3 implementation for additional 3 years, until
2020
Allow industry to spread engineering and construction
projects over 6 years
Allow individual refiners to delay spending

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US Tier 3 Potential Impact on Refinery Operation

Increased FCC pre- or post-treatment operating severity

Reduced catalyst life/cycle lengths more frequent turnarounds
Higher H2 consumption
Reduced gasoline RON
Revamp previous Tier 2 post-treatment investment
Installation of a new pre- or post-treater
Lower cut point and loss of gasoline yield

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Sulfur Balance in a Typical FCC Unit

Feed Sulfur Distribution

Reactor Light Gas: H2S (40%)

Flue Gas 20%-40% reduction
SOx: ~ 5% Gasoline: 5% S in FCC gasoline
sulfur increases
H2S 1%-2% wt%.
LCO: 15% S

Riser Bottoms: 35% S

Sulfides
Thiophenes
Feed Sulfur Benzothiophenes
0.1% 3.0% S Multi-ring Thiophenes

Ap p ro xim a te ly 5% o f FCC Fe e d S u lfu r e n d s u p in FCC g a s o lin e .

FCC g a s o lin e s u lfu r c o n trib u te s 90% o f th e s u lfu r in th e g a s o lin e p o o l.

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Sulfur Species in FCC Gasoline (by GCAED)

Thiophene SH Benzothiophene
Tetrahydrothiophene R
2.8e5
S S
2.7e5
R R
Methylthiophenol
2.6e5
2.5e5 Methylthiophene
Thiophene
2.4e5
Me-THT
2.3e5
C2-Thiophene
2.2e5 Benzenethiol

2.1e5 THT
C2-THT
C2-thiophenol
C3-thiophenes
2.0e5
1.9e5
1.8e5
1.7e5
20 40 60 80 100
Time (min.)
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Reaction Pathways of Sulfur Species in FCC

Sulfur Species in Feedstock Sulfur Species in FCC Gasoline

Multi-Ring Aromatic Thiophenes Minimal

Alkylbenzothiophenes Benzothiophene by dealkylation

Small amount to thiophenols
Alkylthiophenes Thiophenes by dealkylation
Small amount to benzothiophenes
Alkyl Sulfides, Mercaptans Thiophenes by cyclization, aromatization
(including cyclic sulfides)
H2S + Di-Olefin Thiophenes, Mercaptans

Alkylth io p h e n e s a re th e m a jo r c o n trib u tin g s p e c ie s to g a s o lin e s u lfu r

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Gasoline Sulfur Formation Variables and Mechanism

Feed
Sulfur content
Feed type/blend: Coker Gasoil, ATB, VGO
Hydrotreating severity
Catalyst
Gasoline selectivity (catalyst activity)
Hydrogen Transfer functionality
Tower Operation
Gasoline cut point
Reaction Mechanism

S S
k1 k3
R-R + H2S
R R
k2
Thiophene Hydrogen Transfer Tetrahydrothiophene GSR Technology Diolefin

k
Click
1 Basetext
to edit catalyst
styleshydrogen transfer
k3 Catalytic gasoline sulfur reduction technologies
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 Gasoline Sulfur Species Distribution by Feed Type

Comparison of gasoline sulfur species for hydrotreated (H) and

non-hydrotreated (U) feedstocks

Mercaptans & Thiophene

U1 C1 & C2 Thiophenes
C3 & C4 Thiophenes
U2 Benzothiophene
> Benzothiophene
U3
Gasoline ID

Gasoline ID T90 F FBP F

H1 U1 399 472
Total sulfur ranges from 750-1870 ppm
U2 390 484
for the 3 non-hydrotreated feedstocks
H2 U3 444 475
H1 359 423
H3 H2 399 449 Total sulfur ranges from 20-120 ppm for
H3 375 447 the 4 hydrotreated feedstocks
H4 H4 324 401

0% 20% 40% 60% 80% 100% The heavier benzothiophene species are present in all
samples, regardless of feed type
Distribution of Gasoline Sulfur Species

All g a s o lin e s tre a m s will c o n ta in th e s a m e s u lfu r s p e c ie s , b u t in va ryin g a m o u n ts .

Th e re fo re FCC fe e d typ e d o e s n o t im p a c t GS R p e rfo rm a n c e .

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Grace Gasoline Sulfur Reduction (GSR) Products

D-PriSM
Effective at reducing light to intermediate gasoline
sulfur species
Added at 10-15% of catalyst addition rate

GSR 5
Reduces full range gasoline sulfur species
Additive technology based on SuRCA technology
Custom zeolite and matrix formulations for
catalytic cracking

SuRCA
Reduces full range gasoline sulfur species
Catalyst technology tailored to your specific FCCU
yield objectives
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Reaction Mechanism for D-PriSM Sulfur Removal

Active sites = Lewis acid-base pairs

S
H 2S
Chemisorption on Lewis acid sites O Al O

S
+

H
C-S breaking by beta elimination H (6) H
C
S H
(1)
Al O O Al O
O

(1) coordination of THT to strong Lewis

acid/base sites through the sulfur atom H H
S H S (2)

+ H
H
(2) C-S bond breaking by beta -elimination, (5) O Al O O Al O
leading to the formation of a surface
thiolate and an OH group
H H

(3 -4) thiolate could then either desorb as a

S
H (3)
thiol and further react on the surface or (4) O Al O
undergo a second C -S bond breaking by
beta elimination, leading to a surface -SH
group and butadiene

(5 -6) vicinal SH and OH groups could then Mechanism for tetrahydrothiophene decomposition on alumina-based additives.
react, leading to the desorption of H 2S (Reprinted by permission of 2007 Elsevier Inc.)

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Sulfur Reduction by Species Boiling Points

800
A B C D E F
Cumulative Gasoline Sulfur PPM

Base Sulfur

600 D-PriSM
RSH
SuRCA/GSR 5

A Mercaptans <183.5F
400 B Thiophene 183.5F
C1-Thiophenes 186-240F

C Tetrahydrothiophene 241-250F
C2-Thiophenes 251-315F

D Thiophenol & 316-320F

C3-Thiophenes 321-360F
200 E C4-Thiophenes 361-425F
Methylthiophenol 363-366F

F Benzothiophene 426-435F
Alkylbenzothiophenes >436F

0
100 200 300 400 500
Distillation F

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Benefits of Clean Fuels Technologies

FCC Feed Hydrotreater Advantage

Expand feedstock mix flexibility (i.e., run higher S gas oils)
Extend HDT catalyst life cycle (consume all EOR activity)

FCCU Advantage
Reduce gasoline sulfur level of FCC Naphtha
Increase gasoline endpoint (more barrels, constant sulfur)
Manage gasoline pool sulfur during hydrotreater outages

Naphtha Hydrotreater Advantage

Lower sulfur to post treater (preserves octane and reduces severity)
Increase volume to post treater at constant sulfur levels

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Options for Managing Hydrotreater Outage

Decrease rate

Buy lower sulfur crude/gasoil

Take FCC down concurrently

Severely undercut gasoline

The following case study shows how Refinery A utilized GSR

technology to manage their hydrotreater outage while maintaining
compliance with low sulfur fuel regulations.

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GSR 5 Case Study at Refinery A

Refinery A approached Grace 4 months prior to

a scheduled FCC feed hydrotreater shutdown to
help them better understand their options during
the outage.

During the outage the refinery planned to

purchase several hydrotreated feeds, different
to the hydrotreated feed that was routinely used.

Candidate feeds were sent to Grace for analysis

and testing to see the potential effects on FCC
yields and gasoline sulfur.

The candidate feeds were heavier and more

aromatic making them more difficult to crack,
additionally they contained significantly higher
sulfur and nitrogen.

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GSR 5 Case Study at Refinery A

The four feeds were tested using a

representative ecat from Refinery A, and were
shown to reduce conversion by at least 4 wt.%
In addition, the feeds increased gasoline sulfur
between 200-300%.
The refinery concluded that Feed A was too
risky, made the decision to purchase the other
feeds and blend at various ratios with the
available routine feed.
To control gasoline sulfur levels the refinery
trialed Graces GSR 5 additive technology.

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GSR 5 Case Study at Refinery A

Long-Term Profitability Feed Properties

Quick implementation of GSR 5 maximized FCC naphtha
to gasoline pool during FCC feed hydrotreater outage. API 26.4
K Factor 11.7
Higher sulfur FCC feed during outage: SAVINGS $1.7 Sulfur (wt%) 0.1
Million.
Refiner determines GSR 5 profitable for long-term use. Gasoline
Base GSR-5
Sulfur (ppm) 75 55
Ongoing reduced severity operation on FCC
hydrotreater: ANNUAL SAVINGS $8 Million

Refiner Background
Unit Design:
UOP HIGH EFF.
Feed: Hydrotreated VGO
Combustion Mode: Full

Full case study

published in AM-07-06

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SuRCA Case Study at Refinery B

Refinery B is located in Japan.

FCCU processed 45,000 bbl/d of 100%
hydrotreated VGO.
FCCU operated in partial burn.
Trial objective was to meet the Japanese
10 ppm sulfur limits.
Refinery B reached a 53% catalyst
turnover to SuRCA at the end of a 3-
month trial.

SuRCA provided 30-35% gasoline sulfur reduction

When combined with gasoline undercutting, the FCC gasoline could be blended with the balance
of the gasoline pool to achieve <10 ppm gasoline sulfur.
The refinery also used SuRCA to allow a higher FCC gasoline endpoint while maintaining
overall FCC gasoline sulfur.

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 D-PriSM Case Study at Refinery C

Reduced gasoline sulfur 25% - allowed gasoline endpoint increase

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D-PriSM Case Study at Refinery D
Refinery A (UOP Stack) ran D-PriSM to evaluate product capabilities
Very low endpoint gasoline
D-PriSM in inventory reached 8.5 wt%
Metals content on E-cat: ~1500 ppm Ni, ~ 2000 ppm V

Base Period 4% D-PriSM 8% D-PriSM

Feed Sulfur (wt%) 0.71 0.78 0.87

Gasoline Endpoint (F) 390 390 390
Gasoline Sulfur (ppm) 712 593 588
Gasoline Sulfur / Feed Sulfur 0.107 0.080 0.070
Gasoline Sulfur Reduction - 25% 35%
Observed nearly 40% sulfur reduction when combined with mild undercutting

On a normalized basis, 8% D-PriSM achieved 35% reduction

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Summary

Gasoline sulfur reduction catalyst and additive technologies have

been widely accepted by refiners and regulatory agencies as a
cost effective method of gasoline sulfur regulatory compliance
Alone and in combination with hardware solutions
During temporary equipment outages
To provide feedstock flexibility
To limit or recover octane loss due to gasoline post treating
Gasoline sulfur reduction catalyst and additives have been used
in a wide range of applications with up to 40% reduction in
gasoline sulfur
Operating conditions and difference in additive technologies can impact the
level of gasoline sulfur reduction

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Keys to a Successful Clean Fuels Trial

Pre-Trial Planning
Determine level of sulfur reduction desired and timing requirements.
Establish baseline by analysis of pre-trial gasoline and feed samples.
Review current unit operation, PFD, target streams, sulfur balance.
Review logistics for baseload and additive maintenance dose requirements.

Design and Implementation

Select appropriate technology to achieve goals.
Establish a logistics plan: timing, usage rates, multiloader needs.
Analyze gasoline and feed samples at Grace lab and refinery lab.
Sulfur (GCAED and XRF)
Distillation (SIMDIST)
Routine hydrocarbon analysis
Provide pilot plant testing as needed.
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