11 - Advanced Catalytic Olefin-ACO

Advanced Catalytic Olefins (ACO)
A New Process for the Production of

Propylene and Ethylene from Straight Run
Naphtha and Distillates
Curtis Eng
© 2008 KBR, Inc. All Rights Reserved.
Evolution of the Modern Car
1800: Inventor Cugnot invents steam powered car
1800’s Steam
1870: 1st gasoline powered car
Powered Car Early 1900’s, mass production of cars
Tim
elin Bigger cars fueled by oil
1870 1st e
Gasoline
Powered Car Hybrid cars, a
response to a need
Early
Energy Efficient
1900s
Hybrid Car
Bigger &
Better Cars
“Necessity is the mother of invention”

Plato 428BC-348 BC
1
Evolution of Thermal Cracking
1900’s: investigations in thermal cracking for fuels
1920’s: first steam cracker (Union Carbide)
1940-60: advances in technology

1921 Dubbs
Thermal
Cracker TI
M 1960-now: revolutionary advances
E
LI
1925, 1st NE
Commercial
Ethylene Plant
2006: Mega crackers
2010: ACO
1953 KBR
Ethylene Plant ICI
England
1980s KBR
Ethylene Plant-
Idemitsu, Japan
ACO
Reactor
Singapore Olefins Plant

Current State of the Art Thermal Cracking
♦ Breaking and rearrangement of

chemical bonds
♦ High temperatures required, >850C
♦ Overall olefins yields decline with
heavier feeds
♦ Propylene/ethylene (P/E) ratios ~ 0.4-
0.6
0.01 0.40 0.43 0.53 0.58 P/E

Steam Cracking
80
Wt% Yield
60
40 Propylene
20
Ethylene
0
h
h
ne
ne
e
ap
ap
an
ha
.N
ut
.N
op
Et
Lt
vy
Pr
2
Handling of Coke and Heavy Ends is Not a Fun
Activity in Steam Cracking!
A Paradigm Shift – The ACO Process
♦ Development of a CATALYTIC route to

ethylene and propylene
♦ Lower temperatures, ~600-700C
♦ Higher olefins yield with liquid feeds
♦ Very little coke production
♦ P/E ratios of ~1/1
♦ Utilize most common liquid feeds available
(straight run naphtha and distillates)
Advanced Catalytic Olefins (ACO)

3
The Olefins Market
Ethylene Propylene
World Ethylene Demand Forecast World Propylene Demand Forecast
~4% overall growth ~5% overall growth
Million Metric Tons Million Metric Tons
160 100
140 y
y Capacit
120 Capacit 80
100 60
80
60 40
40
20
20
0 0
00 01 02 03 04 05 06 07 08 09 10 00 01 02 03 04 05 06 07 08 09 10
PE Ethylene Oxide EDC EBz Others Polypropylene Cumene Acrylic Acid
Acrylonitrile Oxo Alc Others
(Source: CMAI) Propylene Oxide
Steam cracking will NOT meet future propylene demand
Olefins Regional Issues
Regional Ethylene Growth
% Total Supply
45
35 Americas
Europe
25
15
5 (Source: CMAI)
90 92 94 96 98 00 02 04 06 08 10 12
4
Regional Ethylene Growth
% Total Supply
45 ♦ Highest growth in
Americas Middle East
35
Europe
♦ Ethane feed makes
25
little propylene
Asia Pacific
15 ♦ Asia market also
5
Africa/Middle East increasing
(Source: CMAI)
90 92 94 96 98 00 02 04 06 08 10 12
Propylene Sources
54 KTA in 2000 66 KTA in 2005 89 KTA in 2010
Ethylene Ethylene Ethylene

Plant 66% Plant 65% Plant 57% Refineries
31%
Refineries Refineries
31% 31%
Other 3% Other 4% Other 12%
0.01 0.40 0.43 0.53 0.58 P/E

Steam Cracking
80
Wt% Yield
60
40 Propylene
20
Ethylene
0
h
h
ne
ne
e
ap
ap
an
ha
.N
ut
.N
op
Et
Lt
vy
Pr
5
Regional Ethylene Growth 2004-12 Incremental Olefins Growth
% Total Supply 25000

45 Source: Propylene
Refineries, Nexant
Americas 20000 PERP Report
35
Europe
KTA Olefins
Ethylene
15000 Propylene
25
Asia Pacific 10000
15
Africa/Middle East 5000

5 (Source: CMAI)
90 92 94 96 98 00 02 04 06 08 10 12 0
N America S America W Europe Middle Asia
P/E East Pacific
♦ Highest growth in Middle East Ratios 0.77 0.44 1.5 0.24 0.85
♦ Ethane feed makes little propylene
♦ Asia has very high P/E demand
♦ Asia market also increasing
ACO Process – Why Straight Run Feeds?

Ethylene Production by Feedstocks
Source: CMAI
♦ The majority of global
ethylene is produced
Capacity from liquid feed
♦ Straight run naphtha
is the predominant
feed globally
Greater than 50% of
Ethane Propane Butane Naphtha Gas Oil Others ethylene made from
naphtha
16000
14000
2004-12 Incremental Olefins Growth Widely available
Source: Propylene
♦ Most common feed in
KTA Olefins
12000
Refineries, Nexant
10000 PERP Report
8000 Propylene
Asia (highest P/E
6000 Ethylene ratio)
4000
2000 •Asia has very high P/E

0
demand
East Pacific
6
ACO Process – Uses Naphtha Feeds
Ethylene Production by Feedstocks
Source: CMAI ♦ Straight run naphtha
is the predominant
Production: Millions
Capacity
feed globally
Widely available
Greater than 50% of
ethylene made from
naphtha
2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010
Ethane Propane Butane Naphtha Gas Oil Others
16000
14000
2004-12 Incremental Olefins Growth
0.85 P/E ♦ Naphtha is the most
Source: Propylene
common feed in Asia
KTA Olefins
12000
Refineries, Nexant
10000 PERP Report
8000 Propylene
High P/E ratios required
6000 Ethylene
in Asia
4000
2000
0
East Pacific
What Does This All Mean?
Ethylene growth
Alternative
lower than
propylene
propylene growth
technologies
needed
Steam Crackers
will not meet
Shift to lighter propylene
feeds will give demand
lower P/E
ACO can be a
technology
solution
7
ACO Process Key Features - Reactor
♦ Proprietary KBR FCC

reactor features
♦ Propylene/ethylene (P/E)
Product Ratio ~1/1
♦ Proprietary catalyst from
SK Corporation
♦ All proven hardware and
processes
Straight Run
♦ Robust and flexible,
Naphtha compared to other
processes
Recycle C4-C6
Non Aromatics
ACO Process Key Features - Separation
♦ Product treatment and

R
E Ethylene separation follows ethylene
Reactor C
O
Propylene plant technology
Effluent V Tail gas Compression
E
R BTX gasoline Acid gas removal and drying
Y
Separation and fractionation
to chemical or polymer grade
products
♦ Proprietary expertise for
trace impurities removal
♦ C4s and C5s can be
recycled to reactor with no
further treatment
♦ All proven technology
8
ACO Key Features – Summary
♦ Co-developed by
SKenergy (Korea) and
KBR
♦ Worldwide licensing rights
by KBR
♦ SKenergy will become the
first commercial user of
ACO
Plans underway to install
ACO reactor at the SK #1
Ethylene Unit at Ulsan,
Korea
~2010 startup
SKenergy Background
♦ Large conglomerate
~$24 billion 2006 sales
~5.8 MM t/a products
volume
♦ Very large olefins
facilities
2 KBR steam crackers at
Ulsan
~800 kta ethylene
♦ Regional need for
propylene and high P/E
♦ SK plans to become the
first adopter of ACO
process by 2010
9
SKenergy Experience and Status
♦ Key to ACO is catalyst

Developed by SK R&D
Worldwide patents in
progress
High acid activity tailored to
Zeolite light olefins and LPG
production
High hydrothermal stability
to high temperature steam
♦ Pilot testing conducted at

SK R&D in Daejeon
ACO Catalyst SK pilot plan Fluidized bed reactor
Fractionation recycle
capability
KBR Experience and Status
KBR Fluid Bed ♦ KBR Fluid Cat Cracking

Catalytic Cracking
50+ years
Pilot Plant
Process/
mechanical design
More than 120 units
worldwide
♦ Yield Predictions
Sasol SUPERFLEX
Development & modeling
Feb 2006 KBR in-house and client
feed pilot studies
♦ Sasol SUPERFLEX
Startup and
Commercialization
10
Case Study
♦ Light Straight Run (LSR) Naphtha

♦ Case 1: Conventional Steam Cracker
1000 kta ethylene
~0.5 P/E ratio
♦ Case 2: ACO Process
Maintain same feed rate as Case 1
~1/1 P/E ratio
ACO – Reaction Section
To Flue
Gas System Reactor Effluent
CW
To Recovery
Catalyst Steam Fuel

Fines Oil
BFW
Oil Wash
ACO Tower
Orthoflow Catalyst Storage
Reactor / And Handling
Regenerator
Fresh Feed Recycle
Regeneration
Air
11
ACO Recovery Section
Mix C4/C5/C6 NA
Recycle to Reactor
Coldbox
Light gas
C3 C2
Ref Ethylene
Ref
1-2 Drying 3 Propylene
Treating C2 C3
Splitter Splitter Dehexanizer
Quenched
Gas
Deprop-
anizer
BTX+
Demeth- Deeth-
anizer anizer
Ethane/
Propane
Steam Cracker vs. ACO Overall Yields
Compared to steam cracking

Ethylene Propylene Other
♦ ACO has ~15-20% higher olefins

Steam Cracker, Wt% Yield
yield
♦ ACO has higher P/E of ~1/1
♦ ACO makes more 25% more

BTX
ACO, Wt% Yield
♦ ACO can reprocess all the
C4s/C5 without additional
treating
12
Steam Cracker Yields
Wt%
100
75
Other
Gasoline
50
Propylene
Ethylene
25
0
Steam
Cracker
Steam Cracker vs. ACO Overall Yields
Wt% Compared to Steam Cracker

100
♦ ACO has ~15-20% relatively

75 higher olefins yield
Other
Gasoline
♦ ACO has higher P/E of ~1/1
50
Propylene
Ethylene ♦ ACO makes more 25% more
BTX
25
♦ ACO can recycle all the C4s/C5

0 without additional treating
Steam ACO
Cracker
13
Steam Cracker vs. ACO Cost of Production (COP)
Case 1 Steam Cracker Case 2 ACO

Cost of Production = Cost of Production =
~$730/MT Ethylene $640/MT Ethylene
Feed minus byproduct Feed minus byproduct
Utility & Operation Cost Utility & Operation Cost
Other Costs Other Costs
Depreciation & Profit Depreciation & Profit
ACO Advantages
♦ Converts widely available feeds to ethylene and

propylene
Straight run naphtha, distillates
♦ Higher total light olefins yields compared to steam
cracker
♦ P/E ratio of 1/1 addresses propylene market
♦ More BTX for potential recovery, higher octane
♦ No C4/C5 processing required, all C4/C5 utilized in the
ACO process
♦ Attractive ACO economics compared to steam cracking
♦ CO2 Emissions Lower than the steam cracking case
14
Advanced Catalytic Olefins Process
R
E Ethylene ♦ High growth rates for both
ACO C
O
Propylene ethylene & propylene
Naphtha & Re-
V
E
Tail gas
♦ Ethylene plants will not
BTX gasoline
Distillates cycle R
Y
meeting propylene growth
♦ “Propylene On Purpose”
technologies require niche
feedstocks
♦ Consider ACO Process
Higher overall yields
1/1 P/E ratio
♦ Commercialization plans by
2010 by SK
President Challand and president Shin at signing ceremony
Thank you very much…
Questions?
15

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Advanced Catalytic Olefins (ACO)

A New Process for the Production of

© 2008 KBR, Inc. All Rights Reserved.

Evolution of the Modern Car

1800: Inventor Cugnot invents steam powered car

“Necessity is the mother of invention”

© 2008 KBR, Inc. All Rights Reserved.

1920’s: first steam cracker (Union Carbide)

1940-60: advances in technology

Singapore Olefins Plant

Current State of the Art Thermal Cracking

♦ Breaking and rearrangement of

0.01 0.40 0.43 0.53 0.58 P/E

© 2008 KBR, Inc. All Rights Reserved.

© 2008 KBR, Inc. All Rights Reserved.

A Paradigm Shift – The ACO Process

♦ Development of a CATALYTIC route to

Advanced Catalytic Olefins (ACO)

Steam cracking will NOT meet future propylene demand

© 2008 KBR, Inc. All Rights Reserved.

Olefins Regional Issues

Regional Ethylene Growth

© 2008 KBR, Inc. All Rights Reserved.

Regional Ethylene Growth

© 2008 KBR, Inc. All Rights Reserved.

54 KTA in 2000 66 KTA in 2005 89 KTA in 2010

Ethylene Ethylene Ethylene

Other 3% Other 4% Other 12%

0.01 0.40 0.43 0.53 0.58 P/E

© 2008 KBR, Inc. All Rights Reserved.

Regional Ethylene Growth 2004-12 Incremental Olefins Growth

% Total Supply 25000

Africa/Middle East 5000

© 2008 KBR, Inc. All Rights Reserved.

ACO Process – Why Straight Run Feeds?

2000 •Asia has very high P/E

What Does This All Mean?

♦ Proprietary KBR FCC

© 2008 KBR, Inc. All Rights Reserved.

ACO Process Key Features - Separation

♦ Product treatment and

© 2008 KBR, Inc. All Rights Reserved.

© 2008 KBR, Inc. All Rights Reserved.

© 2008 KBR, Inc. All Rights Reserved.

♦ Key to ACO is catalyst

♦ Pilot testing conducted at

© 2008 KBR, Inc. All Rights Reserved.

KBR Experience and Status

KBR Fluid Bed ♦ KBR Fluid Cat Cracking

© 2008 KBR, Inc. All Rights Reserved.

♦ Light Straight Run (LSR) Naphtha

© 2008 KBR, Inc. All Rights Reserved.

ACO – Reaction Section

Catalyst Steam Fuel

Fresh Feed Recycle

© 2008 KBR, Inc. All Rights Reserved.

© 2008 KBR, Inc. All Rights Reserved.

Steam Cracker vs. ACO Overall Yields

Compared to steam cracking