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©Haldor Topsoe A/S 2017 – all rights reserved
Reducing octane loss -solutions for FCC gasoline post-treatment servicesClaus Brostrøm Nielsen
Haldor Topsoe
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©Haldor Topsoe A/S 2017 – all rights reserved
Agenda
• Why post-treatment of FCC gasoline?
• Molecular understanding of FCC gasoline
• Post-treatment step by step
• Octane loss prediction model
• Haldor Topsoe’s HyOctane Technology (HOTTM)
3
©Haldor Topsoe A/S 2017 – all rights reserved©Haldor Topsoe A/S 2017 – all rights reserved
Why post-treatment of FCC gasoline?
4
©Haldor Topsoe A/S 2017 – all rights reserved
Typical gasoline pool composition
FCC
naphtha
36%
Isomerate
5%
Light SR
gasoline 3%Butanes
5%MTBE
2%
Reformate
34%
Coker
naphtha
1%
Alkylate
12%
Hydrocracked
naphtha 2%
FCC
naphtha
98%
Coker
naphtha
1%
Light SR
naphtha
1%
Percentage of blend stocks of pool volume Distribution of sulfur in blend stocks
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©Haldor Topsoe A/S 2017 – all rights reserved
Why post-treatment?
Gasoline sulfur limits 2016 Gasoline sulfur limits 2020
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©Haldor Topsoe A/S 2017 – all rights reserved
0 100
Octa
ne
lo
ss
HDS conversion (%)
Octane lossGeneral trend
Octane loss increase with increasing sulfur removal
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©Haldor Topsoe A/S 2017 – all rights reserved©Haldor Topsoe A/S 2017 – all rights reserved
Molecular level understandingof FCC naphtha
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©Haldor Topsoe A/S 2017 – all rights reserved
Distribution of sulfur
0
10
20
30
40
50
60
70
80
90
100
0 50 100 150 200 250
Cu
mu
lati
ve
su
lfu
r (%
)
Temperature (°C)
Mercaptans
Thiophene
C1-Thiophene
C2-Thiophene
C3-Thiophene
Benzo-ThiopheneLight CN Heavy CN
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©Haldor Topsoe A/S 2017 – all rights reserved
Distribution of olefins
Light fraction
• High olefin concentration
• Low sulfur concentration
• Mercaptan sulfur
Heavy fraction
• Low olefin concentration
• High sulfur concentration
• Thiophenic sulfur0
2
4
6
8
10
12
14
C4 C5 C6 C7 C8 C9 C10 C11
To
tal
Ole
fin
s (w
t %
)
Carbon number
Light CN Heavy CN
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©Haldor Topsoe A/S 2017 – all rights reserved©Haldor Topsoe A/S 2017 – all rights reserved
Post-treatment step by step
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©Haldor Topsoe A/S 2017 – all rights reserved
Main function of the selective hydrogenation unit
• Selectively hydrogenation of di-olefins• Prevent fouling in downstream HDS reactors
• Transform light sulfur into heavy sulfur• Low sulfur light fraction out of splitter
FCC Naphtha Feed
Sta
bili
zer
HCN
Sp
litte
r
LCN
Ultra low sulfur HCN
HD
S
Me
rca
pta
n C
on
tro
l
Se
lect
ive
hyd
rog
en
ati
on
Light ends
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©Haldor Topsoe A/S 2017 – all rights reserved
FCC naphthaSulfur speciation – SHU feedstock
Light mercaptans
Th
iop
he
ne
C1-Thiophene
C2-Thiophene
C3-Thiophene
Be
nzo
T
hio
ph
en
eHeavy
mercaptans
• Gas chromatogram
• Sulfur specific detector (GC-AED)
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©Haldor Topsoe A/S 2017 – all rights reserved
Pilot plant test, Haldor Topsoe catalyst TK-703 HyOctaneTM
Selective Hydrogenation Unit (SHU), sulfur speciation
Feed Product
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©Haldor Topsoe A/S 2017 – all rights reserved
Pilot plant test, Haldor Topsoe catalyst TK-703 HyOctaneTM
Selective Hydrogenation Unit (SHU), sulfur speciation – product
Light fraction
Heavy fraction
Sulfur free
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©Haldor Topsoe A/S 2017 – all rights reserved©Haldor Topsoe A/S 2017 – all rights reserved
Heavy naphtha desulfurization
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©Haldor Topsoe A/S 2017 – all rights reserved
Hydrodesulfurization of HCNLayout
FCC Naphtha Feed
Sta
bili
zer
HCNS
plit
ter
LCN
Ultra low sulfur HCN
HD
S
Me
rca
pta
n c
on
tro
l
Se
lect
ive
h
ydro
ge
na
tio
n
Light ends
Topsoe’s TK-710 HyOctane™ and TK-747 HyOctaneTM catalysts are well proven in the HDS reactor and the Mercaptan control reactor
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©Haldor Topsoe A/S 2017 – all rights reserved©Haldor Topsoe A/S 2017 – all rights reserved
Octane loss prediction model
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©Haldor Topsoe A/S 2017 – all rights reserved
Octane loss prediction model
Foundation
• Based on molecular understanding
• Large database with detailed chemical analysis (759 components) of commercial and pilot plant feed and product samples
• Intelligent reduction of complexity by the discovery of a manageable number of key reaction paths that govern octane loss
Model flexibility
• Unit design (splitter, number of HDS reactors)
• Final boiling point of feed
• Feed and product sulfur
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©Haldor Topsoe A/S 2017 – all rights reserved
Key reaction path exampleMaking 2-methylpentane
Reactants, average RON = 100
2-methylpentene-1
2-methylpentene-2
4-methylpentene-14-methylpentene-2
(cis and trans)
2-methyl-1,4-pentadiene
2-methylpentane
Product, RON = 76ΔRON = -24
Abundant + high impact
reaction path
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©Haldor Topsoe A/S 2017 – all rights reserved
Model usage
Feed sample for analysis
Process conditions
Octane loss model
Calculated Octane loss
10
ml sa
mp
le
Input Output
Product specs
Unit design
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©Haldor Topsoe A/S 2017 – all rights reserved©Haldor Topsoe A/S 2017 – all rights reserved
The Topsoe HyOctane Technology HOT™ Process
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©Haldor Topsoe A/S 2017 – all rights reserved
The Topsoe HyOctane Technology HOT™ Process
• Deep catalyst understanding
• Deep kinetics and equilibrium understanding
• Extensive pilot work
• Use of process model for octane prediction
• Hydrotreating engineering capabilities
• Invention resulting in unmatched octane retention
The new technology leap
Revamp
Tighten sulfur spec
More olefinic
feed
Higher end point
feed
Higher sulfur feed
New Refinery Configuration Grassroots
Where does it apply
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©Haldor Topsoe A/S 2017 – all rights reserved
Changing operation from 30 to 10 wtppm S gasolineTraditional technology
• Much higher RON loss with your existing process technology
Consequence
Cut feed rateCut end point of feed
And/or
100
150
200
250
300
350
400
450
0 20 40 60 80 100
Feed Naphtha curve
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©Haldor Topsoe A/S 2017 – all rights reserved
0
1
2
3
4
5
6
7
8
9
10
65 70 75 80 85 90 95 100
RO
N lo
ss
% HDS
RON loss vs Sulfur removal
The clear octane advantage with the Topsoe HOT™ processThe octane vs HDS relation
Traditional technology
Topsoe HOT™ process
At a product S
of 10 ppm
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©Haldor Topsoe A/S 2017 – all rights reserved
Conclusion
• Topsoe’ HOT™ process reduces the octane loss for same product sulfur by 50–65%
• No need for reducing end point resulting in higher gasoline production
• Possible to process more higher sulfur crudes
• Possible to reduce the operating severity of the FCC pretreat unit
• Possible to cut deeper into the LCO to make more gasoline
Unmatched octane retention in your gasoline pool
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©Haldor Topsoe A/S 2017 – all rights reserved
Summary
• Sulfur reduction in the gasoline is being regulated to 10 wtppm in many parts of the world
• Sulfur reduction result in additional octane loss
• Haldor Topsoe’s model is capable of calculating the octane loss accurately by looking at the octane loss for each molecule and its reaction pathway
• Our HyOctane™ catalyst portfolio is well proven in today’s gasoline post treatment units
• Haldor Topsoe’s new and innovative HyOctane Technology (HOT™) for grassroot units and revamps will reduce the octane loss by 50–65% at the same product sulfur