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©Haldor Topsoe A/S 2017 – all rights reserved

Reducing octane loss -solutions for FCC gasoline post-treatment servicesClaus Brostrøm Nielsen

[email protected]

Haldor Topsoe

2


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


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

5


Why post-treatment?

Gasoline sulfur limits 2016 Gasoline sulfur limits 2020

6


0 100

Octa

ne

lo

ss

HDS conversion (%)

Octane lossGeneral trend

Octane loss increase with increasing sulfur removal

7


Molecular level understandingof FCC naphtha

8


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

9


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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Post-treatment step by step

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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

12


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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Pilot plant test, Haldor Topsoe catalyst TK-703 HyOctaneTM

Selective Hydrogenation Unit (SHU), sulfur speciation

Feed Product

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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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Heavy naphtha desulfurization

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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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Octane loss prediction model

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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

http://www.sigmaaldrich.com/catalog/product/aldrich/m67303

http://www.google.dk/url?sa=i&rct=j&q=&esrc=s&source=images&cd=&ved=0ahUKEwigsM7RxsTSAhWEGCwKHThFDesQjRwIBw&url=http://www.sigmaaldrich.com/catalog/product/aldrich/292397&bvm=bv.148747831,d.bGg&psig=AFQjCNF7u4zZZnXdPxUWjvE2qZ-yAiTEzQ&ust=1488981541540038


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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


http://www.google.dk/url?sa=i&rct=j&q=&esrc=s&source=images&cd=&ved=0ahUKEwigsM7RxsTSAhWEGCwKHThFDesQjRwIBw&url=http://www.sigmaaldrich.com/catalog/product/aldrich/292397&bvm=bv.148747831,d.bGg&psig=AFQjCNF7u4zZZnXdPxUWjvE2qZ-yAiTEzQ&ust=1488981541540038



http://www.sigmaaldrich.com/catalog/product/aldrich/118710


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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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The Topsoe HyOctane Technology HOT™ Process

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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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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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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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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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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

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FCC naphtha post treatment - Refining Communityrefiningcommunity.com/wp-content/uploads/2017/08/Reducing-Octa… · and product samples •Intelligent reduction of complexity by the