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25 Years of MIDW™ Technology:
Proven Option for Premium Distillate
Production
Mohan Kalyanaraman
Sean Smyth
Tim Hilbert
Madhav Acharya
ExxonMobil Research and
Engineering Company (EMRE)
Richard Smith
UOP LLC
Outline
• Outlook for Transportation Fuel Mix
– Factors influencing Diesel Demand
– Cold Flow Properties of Diesel
• History of Catalytic Fuels Dewaxing at EMRE
• MIDW Technology Overview
– Technology Evolution
– Selected Applications
• EMRE and UOP Alliance
– Process configurations
• Summary
Transportation Fuel Mix
Growth in Demand from 2010 to 2040
Fuel Demand
MBDOE
MBDOE
75
Other
Natural Gas
60
OECD
Fuel Oil
45
Biodiesel
9
6
Diesel
30
3
0
Ethanol
Gasoline
0
2000
Non OECD
12
Jet Fuel
15
15
-3
-6
2020
ExxonMobil 2013 Outlook for Energy
2040
Gasoline
Diesel
Jet Fuel Fuel Oil
Natural
Gas
Other
Diesel Demand Impacted by New
Regulations and Regional Incentives
• Renewed interest in diesel vehicles in North
America for meeting future CAFE standards
• Refiners are dealing with changes in crude slates
with some crudes becoming more waxy
• Refiners around the world are looking for higher
distillate yields and better properties and low
Cloud Point for diesel
• Incentives in place for in country refining to
produce high quality products in some regions
of world
Cold Flow Properties of Diesel
Making winter diesel fuels can be challenging
•
As temperature drops, the wax naturally found in diesel begins to form crystals and
solidify
– Can clog fuel filters / prevent engine startup
•
Cold flow improvements tracked by either cloud point or pour point
– Cloud: Temperature when wax crystals begin to precipitate
– Pour point: Temperature at which oil ceases to flow
• Many different approaches to
improve the Cold Filter Plugging
Point (CFPP) of distillate fuels
- Additives to prevent wax aggregation
- Undercutting, kerosene addition,
crude selection…
- Can be costly and may reduce
diesel / jet yield
• Catalytic dewaxing provides a
unique solution
History of Catalytic Fuels Dewaxing at EMRE
Technology:
– Within Mobil, Development
initiated in 1972; Commercialized
in 1978
– 27 MDDW Units
• MIDW Technology:
– Internal Development work on
hydroisomerization using shapeselective zeolites gained
momentum in 1980 and
Commercialized in 1990
100
300°F+ (150°C+) Yield, Wt-%
•
MDDWTM
MIDW
Technology
90
80
MDDW
Technology
70
60
50
0
20
40
60
80
Cloud Point Reduction, °F
100
MIDW Process Produces High Cetane, Low Pour
Product at High Yields
Dewaxing of Minas 650°F - 1000°F Gas Oil
Product Yield, wt%
Feed
MIDW
MDDW
C1-C4
2.2
16
C5-330°F
8.5
32
330°F+
100
89.3
52
330°F+ Pour Point, °F
115
15
50
Cetane Index,
330° – 650°F
77
• Early work on shape-selective materials showed potential
• Market opportunity: Need for production of high quality distillate
and jet
8
Isomerization Selective Chemistry from ShapeSelective Catalyst
• Isomerization Dewaxing
– Selective isomerization of
n-paraffins
– Iso-paraffins have much
lower freeze point for
same carbon number
compared to n-paraffins
– Low pour/cloud/CFPP
products maintained in
distillate boiling range
– Ultralow CP possible (< 70°C) at moderate
operating temperatures
and high yields
9
MIDW Process for Diesel Dewaxing
•
First commercialized by Mobil Oil Corp.
in 1990
•
Isomerizes waxy N-paraffins in gas oils
•
Proprietary catalyst formulations
•
Flexible process configurations
– Many process configurations have been
commercialized
– Easy to integrate with other technologies
•
Commercially Proven
– A total of 11 units operating, and 6 more
under design or construction
1-Reactor
Configuration
High
Activity
HDT
Beds
Quench
MIDW
Process
Bed
2-Reactor
Configuration
HDT
Rxr
MIDW
Rxr
Quench
High
Activity
HDT
Beds
MIDW
Process
Bed
Optional R2 Bypass
Evolution of MIDW Technology
Sixth
generation
Fifth
generation
Fourth
generation
Third
generation
Second
generation
CATALYST
T95 reduction,
ULSD revamp
Optimized staged
process
Cascade Process
configuration
First unit retrofit
Improved
internals
First
generation
PROCESS/
APPLICATIONS
First gen process
MIDW Catalyst in Low Pressure Operation:
Extract Value from Underutilized HDT
Hydrocracker Product
Cloud point = -10 C
Density = 0.852 (35.2 API)
Color = L0.5
•
•
•
Catalyst
•
•
•
•
LHSV = 2-3
Temperature = 287-343C
2+ winters in operation
EOC limited by product color
M
I
D
W
Unit
Product
•
•
•
•
Cloud point = -35 C
Density = 0.846 (35.6 API)
Color = L1.5
Yield = 94-97 vol%
Base Metal MIDW Catalyst for Diesel
End Point Control and High Yields
Technology Comparison
Pilot Operating Scheme
High Sulfur Feed
Fractionator
Naphtha
Diesel
371C+
bottoms
Unionfining
Unit
MIDW/Unionfining
Process
Unicracking
Unit
Feed
HDTMIDW
Cracking
Dewaxing
API
33.5
39
35.9
Sulfur,
ppm
8600
<10
<10
Cetane
Index
61.3
62.5
57
Cloud
point,
deg C
13
-13
-14
T95,
deg C
386
343
343
89.3
73.7
Diesel,
vol%
EMRE and UOP Alliance for
Premium Fuels
•
EMRE and UOP and signed an alliance agreement in July 2011
– Providing hydrocracking, fuels dewaxing and highquality lubes finishing technology to the refining industry
•
EMRE MIDW™ technology, when combined with
UOP Unionfining™ technologies or Unicracking technologies,
allows production of distillate with low Cold Filter
plugging point with minimal yield loss
•
Rapid industry acceptance with licensing of 4 integrated Unionfining
and MIDW technology complexes in less than 2 years
EMRE and UOP working together to provide synergy –
improving outcome to Refiners
MIDW Process Configurations
Flexible Process Applications
Waxy Feed
0.3% S - 130 ppm N
Moderate S, N
0.2 – 0.9 % S
30% LCO in feed
High S, N
MVGO - HVGO
1.2% S – 1800 ppm N
VGO Feed
Unionfining
Unit
MIDW Unit
Low Pour, High Cetane Diesel
MIDW Unit
Lower Reactor Temperatures
Low Sulfur Distillates
H2S, NH3
Unionfining
Unit
MIDW Unit
Lower Reactor Temperatures
Higher Distillate Yields
H2S, NH3, Distillate
Unicracking
Unit
MIDW Unit
Premium Diesel & Kerosene
Low Pour Point LSHFO
Global Experience in MIDW Technology
Applications
Operational units
Awaiting startup/under design/licensed unit
Continuing to Push the Boundaries on MIDW
Process Applications to Deliver Value
• Very low pressure sweet operation
• End Point Conversion
• Trim dewaxing – MIDW catalyst
drop-in
• Drop-in dewaxing operations in sour
service
– Integration with Hydrocracking
• Retrofit to enable Tight Oil dewaxing
Summary
• MIDW technology enables production of
high volumes of distillates with improved
cold flow properties
• Key focus areas going forward are:
– Tight Oil refining
– Diesel Maximization
• EMRE and UOP alliance allows us to offer
an integrated solution to refiners