Methanol to gasoline(MTG) as a green pathto synthetic fuelsThoa Nguyen, PhD.
Project manager, Chemicals R&D, Haldor Topsøe A/S
10 May 2017
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Outline
• Wood to gasoline demonstration project• The process• The chemistry• Other alternatives to green fuels• Conclusions
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Wood-to-Gasoline Demonstration20-25 bbl/d, Des Plaines, IL, 2010-2014
DOE Award No. DE-EE0002874
Biofuel
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The green gasoline project
• DOE grant: 25 mio. USD• Project team cost share: 10 mio. USD• 2010: preliminary design• 2011: start of procurement• 2012: shakedown tests• 2013: gasoline tests
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The green gasoline project
• 20- 25 bpd gasoline• 1.3 bbl gasoline and 0.2 bbl LPG per dry ton wood• Wood pellets as feed
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Green Gasoline from Wood Using Carbona Gasification and Topsoe TIGAS Processes
OXYGEN
BIOMASS
ASH
GASIFIERTAR REFORMER
BIOMASS
ASH
GASIFIERTAR REFORMER
TAR
REFO
RM
ER
BIOMASS
GASIFIER
ASH
http://www.energy.gov/news2009/releases.htm
GasCleaning
OXYGEN
Entire value chain: biomass in à gasoline out
Biogasoline Demonstration Plant
MeOH/DME Gasoline
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Process Flow Diagram GasolinereactorMeOH Gasoline
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T/d & kg/hPilots
H-ZSM-5
Historical Perspective
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Current MTG Test Facility (Denmark)
8 bpd demonstration facility (Houston, TX)
lb/h Test Facility(Denmark)
TIGAS (Topsøe Improved Gasoline Synthesis)
0.6 bpd pilot facility (Ravnholm, DK)
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• Gasification & Tarreforming (existing)
• Morphysorb® AGR unit(existing)
• Utility units & controlsystem (existing)
• Syngas compression (new)• TIGAS synthesis unit (new)• Gasoline & waste water
tanks (new)
Biofuel facility
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Construction: Zeton workshop
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Transportation: reactor and reactor container
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Construction: lifting
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Construction: roof removal to install the TIGAS container in
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Shakedown test
• Stepwise full-scale operation of each major section at process conditions:• Gasification section (Nov 2012)• Gasification + AGR sections (Dec 2012)• Gasification + AGR + TIGAS (Jan 2013)
• Final commissioning of feedstock delivery system• CO2 supply and purge system, syngas compressor, AGR upgrades, and TIGAS plant operation
• First gasoline production (100 gal)
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Aromatics in gasoline
Hours on stream (full value chain)
Gasoline octaneGasoline reactor temperature profile
Hours on stream (full value chain)Relative bed height
Nor
mal
ized
axia
ltem
pera
ture
Vol%
Wood to Gasoline Demonstration Project
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Complete integrated operation
Limited duration(budget constraints)
MAR 13 OCT/NOV 13 MAR 14
Total gasoline production over period = 9870 gallons
Test #1- #3: summary of results
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Gasoline testing
• Engine emissions testing at Southwest Research Institute• Tested a 80/20 high biomass TIGAS/gasoline blend.• Emission levels better than for conventional gasoline.• Found to be ”substantially similar” to conventional gasoline
• Fleet test• Testing 8 vehicles (EPA Standard Road Cycle)
• 2 Camry (2.5 L PFI),• 2 Corolla (1.8 L PFI)• 2 F-150 (3.5 L V6 EcoBoost®),• 2 Fusion (1.5 L EcoBoost®)
• Commercial gasoline vs. 50% biogasoline blend• Accumulate 75,000 miles per vehicle• Engine inspections• Engine emission tests @ 4000 & 75,000 miles
19 Pseudo-Adiabatic Pilot, Ravnholm
• 290-430°C• 15-20 barg• WHSV = 0.8 – 2.6 h-1 fixed bed• Gasoline reactor: ZSM-5• Cycle length: 10-40 days• Lifetime: 1-2 years
Methanol to gasoline (MTG) GasolinereactorMeOH Gasoline
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MeOH/DME C3H6 (CnH2n) + H2O
C3H6 (CnH2n) + MeOH/DME
CnH2n
CnH2n
CnH2n+2CnH2n+2
CnH2n+2
CnH2n
HC-Pool
Homologation
Dehydrocyclization
MeOH(DME)
+ H2O
+ H2O
Reaction Mechanism
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Cn
Typical TIGAS Product Distribution
P I O N
A
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• Address cold flow properties
• Synthetic gasoline from H-ZSM-5 containsdurene
• Durene freezes at 79.2ºC
• Improve cold flow properties by isomerization
• Octane rating
• In the treatment to reduce durene, octane lossif aromatics are saturated
• Synthetic gasoline is also rich inpseudocumene and one of its isomers hasexcellent octane rating
• Boosting octane by isomerization
Two-fold process objectivesGasoline Upgrading Unit (GUU)
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Other fuel routes
MeOH Gasoline
MeOH/DME Gasoline
GUU
GUU
Methanol togasoline (MTG)
Syngas togasoline (STG)
CH4, WGS, CH3OH, DME, MTH, NH3
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Summary• MTG: direct conversion of methanol to gasoline• Topsøe MTG: TIGAS is a versatile technology for conversion of syngas to gasoline• Economy
• Feasible without subsidy at previously high oil prices
• Co-production of power and fuel• Feasible solution to counteract imbalances• Improves overall system flexibility• Maximizes operator revenue• Simplicity and efficiency makes TIGAS suitable for co-generation
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World largest gasoline plant – TIGAS in Turkmenistan
• 175,000 Nm3/h natural gas• Capacity 1800 ton pr. day (~15,500 BPD) gasoline• To be started up in 2018