On Purpose Production of Butadiene and Propylene

On Purpose Production of
Butadiene and Propylene
Tim Foley
Product Line Manager
UOP LLC, A Honeywell Company
Abu Dhabi International Downstream
11 & 12 May 2015
Abu Dhabi, UAE
A Century of Innovation
in the Oil and Gas Industry
© 2015 UOP LLC. All rights reserved.
UOP 7015B-1
Butadiene Industry Trends
2
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Butadiene is a Byproduct
from Ethylene Cracking
Ethane
Propane
Butane
Naphtha
C4s (BD)
Ethylene
Cracker
Proylene
Ethylene
Other
The C4 byproduct
stream is the source for
butadiene in NA.
The shale effect has
greatly reduced the
volume of C4s
 Ethane cracking has dramatically reduced BD supply
 Ethylene production is increasing, but butadiene production is not
Source: IHS Data
3
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On-Purpose BD Will be Needed
The exact timing depends on several factors,
but global demand will outstrip byproduct supply:
• Crackers in NA have strong economic incentives for light feed
• Some European crackers will crack more LPG as exports
from the U.S. increase
• Shale gas exists globally and will be pursued
• Coal/Methanol-to-Olefins in China (makes no BD)
• Chinese government pushing for more propane and
butane as feed for ethylene production
• Fluctuations in crude oil pricing will affect timing
Based on the global economic outlook, shale energy, forward
looking trade flows, cost curves, and industry intelligence, OPBD
will be needed
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Oxidative Dehydrogenation
Chemistry
Primary Reaction
n-C4H8 + ½ O2  1,3 C4H6 + H2O
1-, 2-cis, and
2-trans butenes
Exothemic
13BD
Equilibrium
highly favors
13BD over 12BD
Typical Reaction Conditions
•
•
•
•
5 -15 steam/butene molar ratio
0.5 -1.3 O2/butene molar ratio (O2 fed as air)
330-650ºC
1 -2 atm
Excess steam
to control exotherm
Low pressure to
minimize coking
Catalysts
• Molybdenum Bismuth
• Ferrite Systems
5
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Timeline of TPC Group
OXO-D® Development
Start
1950’s
Start
1959
Start
1965
Start
1975
Next Generation
Laboratory Units
R&D Laboratory Units
Large Scale Pilot Units
Commercial
OXO-D Unit at TPC Group
5 Licensed OXO-D Plants
New Units
2011 - current
End Late
1970s
Last Run
2004
End Late
1980s
• TPC Group LLC has a long history of OXO-D research and development and
commercial operation with a 350kMTA plant in Houston
• Several generations of catalysts have been developed
• 5 licensed OXO-D plants operated in North America and Europe
• Licensees successfully operated a wide range of downstream BD extraction
technologies such as Furfural, DMF, and Beta-MOP
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TPC / UOP OPBD Approach
• In March, 2014 UOP partnered with TPC Group to offer an up-dated version of the OXO-D
process
- Leverage TPC’s commercial operating and licensing experience
- Leverage TPC and UOP research and development capabilities
 2 pilot plants at TPC
 1 pilot plant and multiple lab scale plants at UOP
• UOP and TPC have jointly worked to improve the economic efficiency of the process. This
includes optimizing operating conditions to achieve better capital efficiency and lower utilities.
- Increased yields at equivalent steam usage
- Reduced water make up via the use of recycled condensed water for steam generation.
- Minimized environmental footprint.
- Utilization of the commercially proven catalyst system.
• Both TPC and UOP will continue coordinated research at their respective facilities in order to
further improve the technology.
• UOP is the exclusive worldwide licensor going forward. The technology is now available for
license
TPC/UOP OXO-D Technology
Pilot Plants
UOP Main Pilot Plant
8
TPC Pilot Plants
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TPC/UOP OXO-D
Process Enhancements
• Leveraged advanced characterization capabilities and expertise
to further fundamental understanding of reaction and
deactivation mechanisms
• Developed a robust two-stage design to increase performance
• Developed enhanced reaction kinetic models
- Validated based on multi-stage pilot plant data and prior commercial experience
• CFD modeling utilized to optimize reactor design
• Conducted further flammability and mixing studies as part of
engineering design for process safety
• Implementation of technology to minimize fouling
• Improved process integration to maximize heat recovery and
minimize waste discharge
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The TPC/UOP OXO-D Process
Stage 1
Reactor
Stage 2
Reactor
Quench
Tower
Aldehyde Aldehyde
Scrubber Stripper
Product
Product
Absorber Degasser Stripper
Vent
Air
Steam
Crude
Butadiene
Butenes
Water
Capable of processing
a range of n-butene
concentrations
10
Significantly
increased
butadiene yield
Improved energy
efficiency
Superior crude
butadiene quality
compared to
conventional
sources
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Integration Options
Feedstock
Cracker
C4’s
BD
Extraction
MTBE
Unit
ParaffinOlefin Sep
(optional)
TPC/UOP
OXO-D
FCC C4’s
Butadiene
Recycle
MTO C4’s
B1 Separation
(optional)
1-Butene
11
TPC/UOP
OXO-D
BD
Extraction
BD
Extraction
(optional)
Butadiene
Butadiene
UOP 7083-11
Propylene Industry Trends
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Tremendous Opportunities in Light Olefins
Light Olefin Demand
350
Million MTA
300
Propylene
Ethylene
250
200
150
100
50
0
2000
2005
2010
2015
2020
 World demand for ethylene and propylene growing (about 4%/yr)
 More than 50 MMTA of additional capacity will be needed by 2020
 Driven primarily by growing middle class in developing regions
Population growth continues to drive demand for products
derived from light olefins
Source: IHS Chemical
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Cracker Feed Slate Swings Past Propylene
Cracker Feeds
Cracker Products
Ethane
Ethylene
E/P Mix
Propylene
LPG
Butadiene
Light
Naphtha
FBR
Naphtha
Steam Cracker
Other C4
By-products
Pygas
Gas Oil
Shift to lower cost, lighter feeds results in decrease in
propylene and heavier olefins, including butadiene
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Tremendous Opportunities in Light Olefins
Light Olefin Supply
Million MTA
280
 Growing share
from “other”
sources other than
steam cracking
and refineries
 Propylene gap
continuing to grow
 Options
for on-purpose
olefin production
include MTO, OCP,
and Oleflex
Propylene - Other
Ethylene - Other
Propylene - Refinery
Propylene - Steam Cracking
Ethylene - Steam Cracking
230
180
130
80
2000
2005
2010
2015
2020
UOP technologies to meet your light olefin market demands
Source: IHS Chemical
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LPG to High Value Olefins
with UOP OleflexTM Process
Feedstocks
H2
Products
Uses
Fiber
Propane
Propylene
Packaging
Propylene
Propane
+
+
Contained
Isobutylene
Isobutane
Contained
Isobutylene
Isobutane
UOP Oleflex Process
High performance
plastic
Gasoline Blending
Components
ETBE
MTBE
Iso-Octane
Synthetic Rubbers & Acrylics
Dedicated and Mixed Unit Applications
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C3 Oleflex Complex
C2-
Byproduct H2
Deethanizer
Oleflex
Unit
Propylene
SHP
P-P Splitter
Depropanizer
C3 LPG
C4+
17
 Selective Hydrogenation Process (SHP) converts
methyl acetylene & propadiene to valuable
propylene
 Elegant & simple solution!
 UOP Oleflex Process is used in 12 of the 19
operating PDH Units today
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Leverage UOP CCR Experience in PDH/BDH
Reactor
Section
C4 Oleflex Unit = 3 Rxs
C3/C4 Oleflex Unit = 3 Rxs
Regeneration
Section
Catalyst Flow
>250 UOP CCR’s in
Operation Today
C
C
R
Dryer
Heater Cells
Rx Effluent
Compressor
Cold Box




18
Positive Pressure / Pt Catalyst
Lower Energy Usage
Fewest & Smallest Reactors
Catalyst Change-Out without Shutdown
H2 Recycle
To Frac
Section
Net
Fresh
Hydrogen
& Recycle
Feed Product Recovery Section
UOP 7015B-18
UOP Oleflex Capacity
12,000
Award, Design or Construction
Commissioned
Olefin Capacity, kMTA
10,000
8,000
13
units
6,000
UOP has been awarded 29 of
the last 34 dehydro projects
worldwide since 2011
World’s Largest PDH at 1000 kmta
and 2 PDH Projects at 750 kmta
propylene capacity
4,000
9
units
2,000
11
units
5
units
5 units
1 unit
0
C3 Dehydro
iC4 Dehydro
C3/iC4 Dehydro
Two recent startups in China – great success!
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Summary
 Demand for on- purpose butadiene and propylene will continue to grow
– Shifting steam cracker feedstock will produce less conventional butadiene
and propylene
 The TPC / UOP Oxo-D Process can close the butadiene gap
– Most efficient on purpose production of butadiene with a
long history of commercial success
– Upgrade your excess n-butylenes to satisfy
increasing market demand for on purpose butadiene
 UOP’s Oleflex Dehydrogenation Technology:
– Lowest capital cost & energy usage results in
lowest operating cost (CCOP) and
highest Return on Investment (ROI)
– Process your propane into
profitable propylene
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