METHANOL TO GASOLINE
(MTG) TECHNOLOGY
An Alternative for Liquid
Fuel Production
Mitch Hindman
ExxonMobil Research & Engineering (EMRE)
World CTL Conference
METHANOL TO GASOLINE
(MTG) TECHNOLOGY
An Alternative for Liquid
Fuel Production
Mitch Hindman
ExxonMobil Research & Engineering (EMRE)
World CTL Conference
AGENDA
• Coal/Biomass to Liquid Fuels Background
• EMRE Methanol to Gasoline Technology
• MTG and Fischer-Tropsch Comparative Analysis
• EMRE MTG Licensing – The MTG Advantage
2
Coal/Biomass TO
LIQUID FUELS
BACKGROUND
OPTIONS FOR COAL LIQUEFACTION
Direct
Liquefaction
Fischer-
Tropsch
Synthesis
Coal /
Biomass
Methanol
Synthesis
“Synthetic
Crude”
CH
3
OH
“F-T Crude”
CO
2
O
2
H
2
O
Coal Gasification
Syngas: H
2
CO
2
O
2
Coal Gasification
Syngas: CO + 2H
2
H
2
O
H
2
Direct
Indirect
4
OPTIONS FOR COAL TO LIQUID FUELS
H
2
Direct
Liquefaction
Fischer-
Tropsch
Synthesis
Gasification
Gasification
Coal /
Biomass
MeOH
Synthesis
Refining
Gasification
MTG
Refining
Liquid
Fuels
5
EMRE METHANOL
TO GASOLINE
TECHNOLOGY
• MTG reactions de-hydrate methanol and
convert the available carbon and hydrogen
into various hydrocarbons
• The “Shape Selective” MTG catalyst limits
the synthesis reactions to 10 carbons
• The result is sulfur free gasoline with a
typical 92 Research Octane
• The first MTG plant was operated in New
Zealand from 1985 to 1997 converting
natural gas to gasoline
EXXONMOBIL MTG TECHNOLOGY
Methanol
Water
Gasoline
7
MTG REACTION PATH
8
2 CH
3
OH
CH
3
OCH
3
+ H
2
0
CH
3
OH, CH3OCH3
Light Olefins
+ H
2
0
Light Olefins
C
5
+ Olefins
Paraffins
Naphthenes
Aromatics
C
5
+ Olefins
Methanol
Di-Methyl Ether
Methanol,
Gasoline
Di-Methyl Ether
MTG YIELDS AND PROPERTIES/COMPOSITION
9
MTG GASOLINE YIELDS
Percent of
Feed
Percent of
Hydrocarbon
Product
Gas
1%
2%
LPG
5%
11%
Gasoline
38%
87%
H
2
O
56%
-
MTG GASOLINE
PROPERTIES/COMPOSITION
Octane, RON
92
Octane, MON
82
(R+M)/2
87
Paraffins, vol%
53
Olefins, vol%
12
Naphthenes, vol%
9
Aromatics, vol%
26
Benzene, vol%
0.3
Sulfur
nil
• Methanol is fed to a fixed bed reactor system where all of the
methanol is converted to hydrocarbon and water
• MTG reactor effluent is separated into gas, raw gasoline and water
• Raw gasoline is separated into LPG, light gasoline & heavy gasoline
• Heavy gasoline is hydro-treated to reduce durene content
• Heavy and light gasoline are re-combined into finished MTG gasoline
EMRE MTG PROCESS
10
EMRE MTG PROCESS FLOW DIAGRAM
LPG
Light
Gasoline
Treated
Gasoline
Heavy
Gasoline
MTG
Reactor
System
(Multiple)
C2-
Stabilized
Gasoline
LPG
DeEthanizer
Stabilizer
Stabilizer
Splitter
HGT
Reactor
Methanol
Purge Gas
Raw
Gasoline
Finished
Gasoline
Blending
H
2
O
11
NEW ZEALAND MTG FACILITY: NEW PLYMOUTH NZ
14,500 BPD plant in New Plymouth New Zealand.
Plant ownership 75% NZ Government and 25% ExxonMobi
l
.
MTG
MTG
SynGas and
SynGas and
MeOH Generation
MeOH Generation
12
• The New Zealand MTG experience demonstrated MTG to be a robust technology
• Daily gasoline yield and octane indicated a very consistent process performance
• After start up the unit ran reliably with an on-stream factor greater than 96%
NEW ZEALAND PLANT OPERATING EXPERIENCE
Initial Startup: October, 1985
> 96% Stream Factor over 7 year period
70%
75%
80%
85%
90%
95%
100%
0
360
720 1080 1440 1800 2160 2520 2880
Elapsed Time, Days
Rx Stream Factor
GASOLINE OCTANE, RON
90
92
94
96
1st Calendar Year
85
90
95
GASOLINE YIELD
WT% OF HC
1st
Calendar
Year
13
• Operability
– Gas phase conventional fixed bed reactors
– On-stream MTG catalyst regeneration and replacement
– Gasoline production is de-coupled from syngas generation and methanol
synthesis -- Improves on-stream factor vs. direct coupled operation
KEY MTG FEATURES
14
• Second Generation Design based on 10 years
learning's from New Zealand operation
• Improved heat integration
• Improved process efficiency
2
ND
GENERATION MTG TECHNOLOGY
Ongoing 2
nd
Generation
MTG Catalyst Research
ExxonMobil is the world leader In
catalyst development and manufacture
15
World’s First Coal to Liquids Plant using MTG
16
• First 2
nd
generation MTG: JAMG plant in Shanxi
Province China
• Start Up; June 2009, 2,500 B/D gasoline
MTG Unit
• DKRW announced in Dec. 2007 the first U.S. CTL plant to utilize MTG in
their 15 KBD Medicine Bow, WY Project
• Synthesis Energy Systems in September, 2008 announced their license for
MTG Technology for a series of global CTL projects
OTHER MTG LICENSES
17
MTG AND FISCHER‐TROPSCH
COMPARATIVE ANALYSIS
FISCHER-TROPSCH
MTG
F-T & MTG COMPARATIVE STOICHIOMETRY
(
CO + 2H
2
)
Î (
-C
1
H
2
-)
+ H
2
O
SYN GAS
Gas &
F-T Liquids
(
CO + 2H
2
)
Î CH
3
OH
Î (
-C
1
H
2
-)
+ H
2
O
SYN GAS
METHANOL
Gas &
MTG Gasoline
19
• F-T yields depend on catalyst, temperature and specific technology
• F-T processes produce a range of hydrocarbons that require refining
processes to convert F-T liquids to conventional fuels
• MTG produces a conventional gasoline and an LPG stream
F-T & MTG COMPONENT YIELDS
Components
Fischer‐Tropsch
Co Catalyst @ 220 C
Fischer‐Tropsch
Fe Catalyst @ 340 C
MTG
Fuel Gas
6
15
1.1
LPG
6
23
10.0
Naphtha
19
36
GASOLINE
88.8
Distillate/Diesel
22
16
Fuel Oil/Wax
46
5
Oxygenates
1
5
Data Sources: Sasol 2004 publication.
20
0
1
2
3
4
5
6
7
8
9
10
2010
2015
2030
MB
/D
Pet. Gasoline
Pet. Diesel
Despite demand shifts to diesel and
ethanol substitution, U.S. projected
to remain heavily dependent on
petroleum gasoline.
(Source: U.S. EIA Annual Energy Outlook 2010))
Based on energy content, U.S. &
Europe prices have consistently
provided gasoline a premium over
diesel
(Source: U.S. EIA,
http://www.eia.doe.gov/state/state-energy-profiles-
more-prices.cfm
;
http://www.eia.doe.gov/emeu/international/prices.html#
Gasoline @ 5.25 MBTU/BBL, Diesel @ 5.83 MBTU/BBL: Transportation
Energy Data Book)
U.S. PETROLEUM FUEL DEMAND
Gasoline - Diesel Price ($/MBTU)
Gasoline vs. Diesel as Synthesis Product
(3.5)
(3.0)
(2.5)
(2.0)
(1.5)
(1.0)
(0.5)
0.0
0.5
1.0
1.5
2.0
19
96
19
97
19
98
19
99
20
00
20
01
20
02
20
03
20
04
20
05
20
06
20
07
20
08
20
09
20
10
$/
M
B
T
U
FRANCE
Germany
U.S.
• Joint Study by the U.S. National Academy of Sciences and
National Academy of Engineering as part of the America
Energy Future Project
• Study included a comparative analysis of MTG and Fischer-
Tropsch as alternatives for coal/biomass to liquid fuels
– 50,000 bpd of transportation fuel; i.e. gasoline (no naphtha) and/or diesel
– Light fractions recycled for conversion or electric power
– Study considered impact of Carbon Capture and Sequestration
2009 STUDY:LIQUID TRANSPORTATION FUELS FROM
COAL / BIOMASS*
*Liquid Transportation Fuels from Coal / Biomass: Technological Status, Costs and Environmental Impact,
ISBN: 0-309-13713-6, http://www.nap.edu/catalog/12620.html
22
• The study indicated the MTG based plant had slightly higher overall efficiency
and lower construction costs
• CO
2
Sequestration lowered efficiency by about 1.5% and raised costs 1.5-2%
Fischer-Tropsch
No CO
2
Capture
Fischer-Tropsch
With CO
2
Capture
MTG
No CO
2
Capture
MTG
With
CO
2
Capture
INPUT
Coal, tpd (as received)
26,700
26,700
22,900
23,200
OUTPUTS
Diesel, bpd
28,700
28,700
Gasoline, bpd
21,290
21,290
50,000
50,000
Total Liquid Fuel, bpd
50,000
50,000
50,000
50,000
Electricity, MW
e
427
317
145
111
THERMAL EFF. (LHV)
49.1%
47.6%
54.2%
52.9%
TOTAL PLANT COST ($M)
4,880
4,950
3,940
4,020
TOTAL PLANT COST ($K/bpd)
97.6
98.9
78.8
80.4
EST. BREAKEVEN CRUDE PRICE ($/BBL)
56
68
47
51
2009 NRC STUDY:
LIQUID TRANSPORTATION FUELS FROM COAL / BIOMASS
F-T & MTG ECONOMIC
COMPARISON
Data Sources: Liquid Transportation Fuels from Coal and Biomass, © National Academy of Sciences, 2009; http//www.nap.edu/catalog/12620.html
23
MTG
Licensing
EMRE/Uhde Partnership Provides Full Range of Project
Services
Gasification
Gasoline
MTG
Methanol
Coal/Biomass
•
EMRE Licenses Methanol to Gasoline
Technology
•
EMRE provides basic engineering
design package for licensees to
perform detailed engineering design
and construction.
•
EMRE provides catalysts for the
MTG process.
•
EMRE provides assistance for MTG
start-up and troubleshooting.
•
Uhde provides feasibility studies for the
entire process of clean gasoline
production from coal.
•
Uhde Licenses PRENFLO Gasification
technology
•
Uhde can support other CTL/BTL
technologies to meet customer’s
specific needs
•
Uhde can provide a range of
engineering, procurement and
construction services