METHANOL TO GASOLINE (MTG) TECHNOLOGY An Alternative for Liquid Fuel Production El-Mekki El-Malki and Mitch Hindman ExxonMobil Research & Engineering Company (EMRE) GTL North America Houston, March 12- 13, 2014 Research and Engineering AGENDA • Organic feedstock Conversion to Liquid Fuels • EMRE Methanol to Gasoline (MTG) Technology • Commercial Experience • Key Project Considerations • MTG Technology Licensing 1 1 Organic Feedstock Conversion to Liquid Fuels Research and Engineering Options For Coal Liquefaction O2 H2O CO2 Coal Gasification Syngas: CO + 2H2 Indirect Coal Direct Coal Gasification Syngas: H2 O2 H2O Methanol Synthesis CH3OH FischerTropsch Synthesis “F-T Crude” Direct Liquefaction “Synthetic Crude” H2 CO2 3 Coal To Liquid Fuels Gasification Gasification MeOH Synthesis FischerTropsch Synthesis MTG Refining Liquid Fuels Coal H2 Gasification Direct Liquefaction 4 Refining Natural Gas To Liquid Fuels O2 Natural Gas CO2 H2O Reforming: Syngas: CO + 2H2 Heat 5 Methanol Synthesis Methanol To Gasoline FischerTropsch Synthesis Refining to Jet /Diesel / Other EMRE Methanol to Gasoline Technology Research and Engineering ExxonMobil MTG Technology • Chemistry of methanol conversion to gasoline (MTG) by ZSM-5 zeolite catalyst discovered in the early 1970’s • MTG reactions de-hydrate methanol and convert the available carbon and hydrogen into hydrocarbons • The “Shape Selective” MTG catalyst limits the synthesis reactions to ~ 11 carbons • Process designs for MTG were developed during the 1970’s and 1980’s • The result was selection of a fixed bed process that produced sulfur free gasoline with 92 RON Octane • The fixed bed design was first commercialized in New Zealand in 1985 converting natural gas to gasoline 7 Fixed Bed MTG Pilot 100 B/D Fluidized-Bed MTG Methanol to Gasoline Chemistry 2 CH3OH CH3OCH3 + H20 Methanol Di-Methyl Ether Light Olefins + H20 CH3OH, CH3OCH3 Methanol, Di-Methyl Ether Light Olefins C5+ Olefins C5+ Olefins Paraffins Naphthenes Aromatics Gasoline Catalyst & process design are key to high yield and gasoline selectivity 8 Typical MTG Product and F-T Synthesis Crude MTG Hydrocarbons • MTG produces a bi-modal distribution of mixed hydrocarbons • The product mix is limited to LPG and sulfur free high octane gasoline Typical Low Temp F-T Syn Crude • F-T reactions typically produce a broad spectrum of linear hydrocarbons referred to as F-T Synthesis Crude • F-T Synthesis crude is refined into sulfur free fuels, lubes or chemical feed stocks 9 EMRE Fixed Bed MTG Process: MTG Reactor Section Basic MTG Process Flow • Methanol is vaporized by heat from the MTG reaction and fed into a DME reactor • DME reactor effluent is mixed with MeOH recycle gas & fed to the MTG reactors • Recycle gas controls reactor temperatures • MTG reactor effluent is cooled by the methanol feed, recycle gas & air or water • Condensed effluent is separated into gasoline, water and gas • Raw gasoline is pumped to a recovery section DME MTG Raw Gasoline To Recovery Section Water 10 EMRE Fixed Bed MTG Process: Raw Gasoline Recovery Section • Raw MTG gasoline is fed to de-ethanizer and stabilizer columns to remove fuel gas and LPG fractions from the gasoline • Stabilized gasoline is split into light and heavy gasoline fractions • Heavy gasoline is mildly hydro-treated to reduce Durene (1,2,4,5 tetra-methyl benzene) content • Treated heavy gasoline and light gasoline or blended into finished product 11 MTG Process Yields and Properties/Composition MTG GASOLINE PROPERTIES/COMPOSITION MTG GASOLINE YIELDS Gas LPG Percent of Feed Percent of Hydrocarbon Product 1% 2% 5% 11% Octane, RON 92 Octane, MON 82 (R+M)/2 87 Paraffins, vol% 53 Olefins, vol% 12 Naphthenes, vol% Gasoline H2O 38% 56% 87% 12 9 Aromatics, vol% 26 Benzene, vol% 0.3 Sulfur nil Commercial Experience Research and Engineering The World’s Commercial Scale Gas to Liquid Plant Methanol to Gasoline -- MTG Gas Reforming and Methanol Synthesis • The 14,500 BPD New Zealand Synfuels plant started up in 1985 • Plant produced on-specs gasoline within 24hrs of start-up • The plant was operated by New Zealand Synfuels until 1995 14 Modular Construction Of New Zealand Plant • Maximum Module • 33 by 15 Meters • 600 tonnes • Total Lift • 66 Modules • 15,000 tonnes 15 New Zealand MTG Fixed Bed Reactor Loading the Fixed Bed MTG Reactor 16 New Zealand Finished Gasoline Quality Average Range Octane Number, RON 92.2 92.0 – 92.5 Octane Number, MON 82.6 82.2 – 83.0 Reid Vapor Pressure, kPa 85 82 – 90 Density, kg/m3 730 728 – 733 Induction Period, min. 325 260 – 370 Durene Content, wt% 2.0 1.74 – 2.29 % Evaporation at 70° C 31.5 29.5 – 34.5 % Evaporation at 100° C 53.2 51.5 – 55.5 % Evaporation at 180° C 94.9 94 – 96.5 End Point, °C 204.5 196 - 209 Distillation 17 New Zealand Plant Reliability Rx Stream Factor Initial Startup: October, 1985 100% 95% 90% 85% 80% 75% 70% 0 360 720 1080 1440 1800 2160 2520 2880 Elapsed Time, Days • The New Zealand MTG experience demonstrated MTG to be a robust technology • After start up, the unit ran reliably with an on-stream factor greater than 96% over 7 year period 18 World’s First Coal to Liquids Plant using MTG Technology In 2009, Jincheng Anthracite Mining Group (JAMG) plant in Shanxi Province China became the first 2nd generation MTG Plant; 2,500 Barrels per day of Gasoline MTG Unit JAMG executed a new MTG License with EMRE in September, 2011 for 25,000 Barrels per day of MTG Gasoline Capacity 19 JAMG MTG Unit 2,500 B/D 20 Key MTG Process Features • Gas phase conventional fixed bed reactors − Design & Construction simplicity − Scalability (2.5 kBD – 14.5 kBD) • Single liquid phase fuel product • On-stream MTG catalyst regeneration and replacement 21 Current MTG Licenses • JAMG, Shanxi Province China, 2,500 B/D, CTL, S/U in 2009 • DKRW, Wyoming, USA, 15 KBD, CTL, EPC phase start in 2013 • Synthesis Energy Systems, West Virginia, USA, CTL project on hold • JAMG, Shanxi Province China, 25 KBD (2 x 12.5 KBD), CTL, Under Construction • Sundrop Fuel, Louisiana, USA, 3.5 KBD GTL/BTL, EPC expected 2014 • G2X Energy: Multi-License Gas to Gasoline Agreement Lake Charles, LA, USA, 12.5 KBD, feasibility phase in 2013-2014 22 Key Project Considerations Research and Engineering Key Project Considerations Technical Risk • Coal and Gas conversion to Methanol and Methanol conversion to Gasoline are commercially proven Simplicity • MTG produces a single marketable gasoline fuel.... No “refinery” needed to make marketable fuels Constructability • Uses gas phase conventional fixed bed reactors • Modular construction demonstrated in New Zealand MTG Operability • Moderate to low temperatures / pressures • Gasification and methanol synthesis decoupled from gasoline production High MTG on-stream factor MTG unit sized for calendar day methanol production 24 MTG Technology Licensing Research and Engineering MTG Technology Licensing • EMRE Licenses Methanol to Gasoline Technology • EMRE provides a basic engineering design package for Licensees to perform engineering design and construction • ExxonMobil Catalyst Technologies provides catalysts for the MTG Process • EMRE Provides assistance as needed of EPC, Start-up and ongoing operations support 26 The World’s First Commercial Scale Gas to Liquid Plant Thank You 27
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