What can be done with

Pyrolysis Gasoline
Quentin Debuisschert
Isabelle Conso
Arno Fritz

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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 Content

• Hydrogenation Technology Update

• Catalysts Portfolio Update
• Grassroots Upgrading Strategy
• Revamping Upgrading Strategy
• Commercial Experience
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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 Axens
Fully Integrated Services

RSI July 1, 2001

Eurecat Procatalyse
IFP
Licensing

IFP School Prosernat

Axens Core Business: Licensing, Catalysts, Services

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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 Content

• Hydrogenation Technology Update

• Catalysts Portfolio Update
• Grassroots Upgrading Strategy
• Revamping Upgrading Strategy
• Commercial Experience
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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 Pygas Characteristics

Typical composition of C5 - 200 °C Pyrolysis Gasoline

wt
wt%%
Paraffins
Paraffins 88––12
12
Aromatics
Aromatics 58
58––62
62
Olefins
Olefins 88––10
10
Diolefins
Diolefins 18
18––22
22
Total
Totalsulfur
sulfur 50
50--300
300ppm
ppm

• High Potential for Aromatics/Bz Upgrading

• Potential for Mogas Upgrading
• Sulfur Removal required in Any Case
• Very Unstable Material – SHU Required 5
ERTC Petrochemical Conference, 3-5 march 2003, Paris
 SHU - First Stage Hydrogenation Process

First Stage
Selective
Hydrogenation To Second
SHU Stage HDS

Make-Up
Hydrogen To
CW CW
Stabilizer

RPG

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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 SHU (First Stage) Process Features

• Moderate Temperature/Pressure: 50-150oC / 25-30 bar

• Liquid Phase Operation Ensures Long Cycles

• Temperature Control with Liquid Quench/Diluent

• Hot Separator Temperature Increases Energy Savings

• Chamber-Type Reactor with Special Internals

• High Diolefins/Alkenyl Aromatics Removal

• Olefins Saturation Control, No aromatics Loss

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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 HDS - Second Stage Process
Second Stage
Fuel Gas
HDS

Trim To
Heater Stabilizer
Make-Up
Hydrogen

CW

RPG

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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 HDS (Second Stage) Process Features

• Moderate Pressure: 25-30 bar

• Dual Catalyst System
• Vapor Phase Reaction, Temp. Profile Control
• Chamber-Type Reactor with Special Internals
• Long Cycles through Active Catalysts and SHU
• Ultra Low Sulfur in Product ( Aromatics and Mogas)
• Olefins Removal – Aromatics Preservation
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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 Technology Update

• Axens World Leader in Pygas Hydrogenation

• Over 30 years Industrial Experience
• Large Operating/Troubleshooting Experience
• Contaminant Expertise
• Over Last 3 Years on Pygas SHU/HDS
- Launching of New Catalyst Generation
- Development of New Internals
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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 Technology Update

• Heavy Involvement in FCC Gasoline SHU/HDS

• Commercialization of Prime-G+
• 70 references in 3 years – World Leader
• Prime-G+ Success translated into:
- Enhanced Operating Experience

- Improved Internals (SHU and HDS)

- New Catalyst Generation under Development

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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 Prime-G+ Process
10-50 ppm Sulfur Spec

Prime-G+
Ultra Low S LCN to
Selective
Pool, TAME or Alky Unit
Hydrogenation
Splitter

Prime-G+
Dual Catalyst
FRCN Reactor System
Ultra-Low
HCN Sulfur
60°C + Gasoline
H2 Make-up
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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 Content

• Hydrogenation Technology Update

• Catalysts Portfolio Update
• Grassroots Upgrading Strategy
• Revamping Upgrading Strategy
• Commercial Experience
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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 New SHU Catalyst Series Launching

• LD-365 Pd based Catalyst

- 50 % Higher Activity than LD-265
- Higher Sulfur Tolerance
- Commercially Proven
- Long Term Feedback
• LD-341 Ni based Catalyst
- Activity Similar to LD-265
- 100 % Higher activity than LD-241
- Very High Resistance to Poisons
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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 Pygas SHU (1st Stage)
New Generation Pd Catalysts

• LD 365 Industrial Operation

LD 365 Styrene Conversion (%)
100

90

80

LD 265 main styrene conversion

70

60

50
0 50 100 150 200 250 300 350
Days on stream

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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 Pygas SHU (1st Stage)
New Generation LD365 Pd catalyst

End of Cycle Due to Olefin Plant Shutdown

Customer’s EOR Criterion
LD 365
Reactor
Inlet T
LD 265 End of Cycle

0 100 200 300 400

ERTC Petrochemical Conference, 3-5 march 2003, Paris Days on Stream 16

 Catalyst Portfolio
SHU – Ni and Pd Performance

Relative Relative Cycle Length,

Catalyst Metal Activity per LHSV Years*
Volume

LD 241 Ni 1 1 0.5
LD 265 Pd 2 1.5 - 2 0.8 - 1.5
LD 341 Ni 2 1.5 - 2 0.8 - 1.5
LD 365 Pd 3 2.5 - 3 1-2

* for Full Range C5 - 200oC Pyrolysis Gasoline

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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 SHU Catalyst Portfolio Strategy

Previous New
Case Catalyst Catalyst

Unit revamp
Up to 150% Capacity LD 265 LD 365
LD 241 LD 341
New Feed with Contaminants LD 265 LD 341
Grassroots unit
Uncontaminated Feed LD 365/341
Contaminated Feed LD 341

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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 Palladium/Nickel Price Differential

London Palladium Price, London Nickel Price,

$/ounce $/ton

1988 1990 1992 1994 1996 1998 2000 2002

Source:Kitco
116 $/oz Jan 1996 23 900 $/ton Apr 1998
1 080 $/oz Jan 2001 7 140 $/ton Jan 2001
400 $/oz (15$/g) Jan 2002 5 050 $/ton Jan 2002

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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 New Generation of HDS Catalysts

• First Catalyst: Dedicated to Olefins Hydrogenation

(LD 145) Avoids Bed Plugging and Pressure
Drop Build-up
• Second Catalyst: Highly Active and Selective
Low Product Sulfur and Olefins
No Aromatics Loss
Relative Cycle Length,
Catalyst Metal Activity per Years*
Volume
HR306 CoMo 1 3
HR406 CoMo 1.5 4
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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 Content

• Hydrogenation Technology Update

• Catalysts Portfolio Update
• Grassroots Upgrading Strategy
• Revamping Upgrading Strategy
• Commercial Experience
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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 Steam Cracker C5’s Upgrading

• High Diolefins Content

- Valuable Diolefins: CPD, Isoprene
- DCPD Production and Isoprene Extraction
• Significant Olefins Content
- Limitation for Mogas Pool Incorporation (RVP)
- Hydrogenation required for Recycle to Cracker
Full hydrogenation in mixture with C6+
Dedicated C5 Hydrogenation (+C4’s)
Deep Hydrogenation in SHU
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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 C5 Olefins Total Conversion
C5’s Recycle to Cracker

F. G. C5s
Raw H2S Recycle to
Pygas Cracker
C5-C8
1st Stage 2nd Stage
SHU HDS

Olefins < 0.05wt% C6 – C8

Aromatics

Cycles > 3.5 years

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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 C5 Olefins Total Conversion
C5’s Recycle to Cracker

225

200

175
Br Index Cycle 1 Br Index Cycle 2
150
Bromine
Index, 125

mg/100g 100

75

50

25

0
0 1 2 3 4

Year in Operation
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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 C5 Olefins Deep Hydrogenation
In Dedicated unit
Raw C4s
(Optional)

C5s Axens C4/C5 Recycle to Steam-

Hydrogenation
Raw Cracker
Pyrolysis
Gasoline Olefin Saturation > 90%
Commercial Experience
C4’s Co-processing

C6+ Raw Pyrolysis Gasoline to

Hydrogenation-Aromatics plant

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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 C5 Olefins Deep Hydrogenation
SHU at Maximum Severity

F.G.

C5s to Cracker
Furnaces
High Severity
SHU

Raw
Pyrolysis
Gasoline C6 + to HDS

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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 SHU at Maximum Severity

C5 Olefins Saturation by Temperature increase

Initial Inlet T Inlet T + 30 °C

N-Pentenes Base Base * 2.5

Cyclo-Pentene Base Base * 2.0
Iso-Pentenes Base Base * 10

65 % C5 Olefins Saturation by 30 °C T Increase

BUT Significant Reduction in Cycle

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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 SHU at Maximum Severity

SHU Revamping + High Activity LD365 Catalyst

Previous Revamping +
Operation High Activity Cat.

Capacity Base Base

WABT Base Base
C5 Cut BrN 120-130 75-80

On-Going Cycle: 14 months

Revamping Option more profitable than new
unit on C5’s
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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 Steam Cracker C7+ Upgrading

• Aromatics Production
- Co-Processing with C6 Cut in HDS before
Extraction
• Motor Gasoline Upgrading
- Excellent Octane but
- High Aromatics (> 35 %) and Sulfur (> 10 ppm)
- Requires HDS in Any Case
• Other Options
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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 Benzene Production coupled with
On-Spec Gasoline Production
C5s to Steam-Cracking Furnaces

Cycle> 12 months
Styrene<0.05wt% Fuel Fuel Gas C6s to
Gas H2S Benzene
Extraction
Raw S < 1 ppm
Pyrolysis
Gasoline 22nd
nd

Pygas
Pygas Stage
Stage
SHU
SHU HDS
HDS

C7+ to Mogas
Pool
C6+ Aromatics S < 10 ppm
S<5 wppm
ERTC Petrochemical Conference, 3-5 march 2003, Paris Bz recovery>99.5%
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 Benzene Production coupled with
On-Spec Gasoline Production
Temperature,°C Styrene Content In Effluent, Wt%
Base + 100
0.16

Base + 60
0.12

Base + 40
0.08

Base
Effluent 0.04
Styrene
Conc.
0.0
6 7 8 9 10 11 12 13
Months from the Start-Up
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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 Upgrading C7+ fraction
for Ultra Low Sulfur Gasoline Pool
• Actual configuration :
- C6 or C6-C8 to Aromatics
- C7-C8 + to Mogas Pool – Off-Spec in the future
• Three solutions :
- Revamp of Existing C6 HDS unit co-processing C7+
- New HDS unit to Process C7+
- Co-Process with FCC Gasoline in Prime-G+ Unit
• Problems with Highly Unstable C7+ Cut
- Transport/Storage/Styrenics Management
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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 HDS Catalyst Stability on C7+ Unstable Cuts

HDS
Catalyst
WABT

0 100 200 300 400 500

Days on Stream

Prime-G+ HDS Co-processing C7+ Pygas

No Deactivation after 1 ½ year
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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 Pressure Drop Management
C7+ Unstable Cuts

0.8

0.6
Normalized DP,
(Bar)/(Flowrate)2
0.4

0.2

130 180 230 280 330 380

Days on Stream

Prime-G+ HDS Co-processing C7+ Pygas

No Pressure Drop Build-up after 1 ½ year 34
ERTC Petrochemical Conference, 3-5 march 2003, Paris
 Content

• Hydrogenation Technology Update

• Catalysts Portfolio Update
• Grassroots Upgrading Strategy
• Revamping Upgrading Strategy
• Commercial Experience
35
ERTC Petrochemical Conference, 3-5 march 2003, Paris
 Revamping Strategy Requirements
• Units already in Place
• Capacity Increase Requirements
• Unit Economics Improvement
- Higher On-Stream Time
- More Severe Specifications
• Processing of Contaminated Feedstocks
- Imported Material
- Condensates Feed to Cracker
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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 Revamped Unit Configuration
Fractionator Recycle Fuel Gas
Gas

Pygas
Feed BTX
Sulfolane
Extraction

C9+

First Stage Second Stage Stripper

SHU Reactor HDS Reactor
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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 Revamping Industrial Experience

Unit Revamping + High Activity LD365 Catalyst

SHU Reactor Cycle Length

Inlet T years

Before 1988 Base 1

1988-1998 LD265 Base – 50 % 2
1998+ Rev. + LD365 Base – 70 % 4

Effectiveness of Revamping
Severe Specifications
Extremely Long Cycles
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ERTC Petrochemical Conference, 3-5 march 2003, Paris
 Revamping Industrial Experience
Temperature, °C
Base + 300
HDS Reactor Outlet
Base + 250

Base + 200
HDS Reactor Inlet
Base + 150
SHU Reactor Outlet
Base + 100

Base + 50

Base
SHU Reactor Inlet
Base - 50
SOR SOR + 6 SOR + 12 SOR + 18 SOR + 24
Months on Stream from Start-of-Run (SOR) 39
ERTC Petrochemical Conference, 3-5 march 2003, Paris
 Contaminated Feedstock
Replacement of Pd Cat. by LD341

Contaminated Feedstock: As (50-300 ppb), Si, Hg

Palladium Axens
Catalyst LD341

Styrene in Product, w% < 0.3 < 0.3

Cycle Length Base Base * 5

Industrial Experience in Asia

Effectiveness of Cat. Replacement by LD341
Significantly Improved Unit Reliability and
Economics 40
ERTC Petrochemical Conference, 3-5 march 2003, Paris
 General Conclusion

• Axens Leading Position in Steam Cracker Effluents

Hydrogenations (C3, C4, Pygas)
• Unrivaled Industrial Experience (500 references)
• Schemes Optimization and Revamping Experience
• Continuous Efforts in R and D
• Large Catalyst Portfolio
• High Efficiency Internals
• Cost Effective and Reliable Technologies
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ERTC Petrochemical Conference, 3-5 march 2003, Paris