Energy-related research at CVT... and methanol-based technology INSTITUTE OF CHEMICAL PROCESS ENGINEERING CVT (KIT Campus South) B. Kraushaar-Czarnetzki 1st Workshop of the Helmholtz Research School Energy-Related Catalysis November 2010 KIT University of the State of Baden-Wuerttemberg and National Research Center of the Helmholtz Association www.kit.edu
Outline CVT Profile process engineering catalysis processes under investigation energy-related projects Fuels from syngas Formation of methanol and DME Olefins formation from MeOH/DME conversion to fuels Formation of gasoline from MeOH/DME Chemistry of MTG and MTO Related research at CVT 2 Prof. Dr. B. Kraushaar-Czarnetzki
CVT Profile (I): Process Engineering experimental reactor evaluation membrane reactors microreactors design & construction of research reactors & units Process process simulation reactor modelling process kinetics processing and novel processing concepts 3 Prof. Dr. B. Kraushaar-Czarnetzki
CVT Profile (II): Process Engineering TIC TIC TIC Abgas left: Taylor-Vortex-Reactor reactions in liquids L/L, L/L/S, L/G, L/S/G low macroscopic backmixing intensive micromixing, if desired several axial feedpoints NV TI TI, PI Analyse TIC TI, PI right: multisampling reactor single tube in multitub. reactor adjustable axial T-profile G/S, for particles & packings monitoring of axial C i -profiles Edukte TIC TIC TIC TIC TIC VZ R TI TI TI TI TI TI, PI TIC TI, PI TI, PI TI, PI TI, PI MPV 4 Prof. Dr. B. Kraushaar-Czarnetzki
CVT Profile (III): Catalysis synthesis mechanisms functional characterization molecular modelling Catalyst kinetic modelling spectroscopy & surface science basic characterization formulation & shaping 5 Prof. Dr. B. Kraushaar-Czarnetzki
CVT Profile (IV): Processes Processes under investigation Selective Oxidations methane formaldehyde o-xylene phthalic anhydride PROX (CO in H 2 ) propene propane propene butane butenes acrolein acrylic acid propylene oxide maleic anhydride maleic anhydride raffinate II maleic anhydride Other Reactions MTO (methanol to olefins) MTG (methanol to gasoline) syngas to gasoline hydrocacking & hydroisomerisation aromatics hydrogenation maleate THF (single stage) acetone MIBK (single stage) isomerisation (supercritical) in blue: finalised, much of experience present 6 Prof. Dr. B. Kraushaar-Czarnetzki
CVT Profile (V): Processes Energy-related projects Selective Oxidations methane formaldehyde o-xylene phthalic anhydride PROX (CO in H 2 ) propene propane propene butane butenes acrolein acrylic acid propylene oxide maleic anhydride maleic anhydride raffinate II maleic anhydride Other Reactions MTO (methanol to olefins) MTG (methanol to gasoline) syngas to gasoline hydrocacking & hydroisomerisation aromatics hydrogenation maleate THF (single stage) acetone MIBK (single stage) isomerisation (supercritical) 7 Prof. Dr. B. Kraushaar-Czarnetzki
CVT Profile (VI): Energy-Related Projects Partial oxidation of methane in a microreactor Project leader: Stephanie Renz Collaboration with IMVT (Dr.-Ing. Peter Pfeifer) Funded by Start-Up Budget (KIT) and Helmholtz Research School See Steffi's poster! Look at posters by Anier and Kyra! Hydroprocessing of dodecane (model feed) at Fischer-Tropsch conditions Project leader: Anier Freitez Collaboration with EBI (Prof. Georg Schaub, Kyra Pabst) Funded by DFG 8 Prof. Dr. B. Kraushaar-Czarnetzki
CVT Profile (VII): Energy-Related Projects Preferential oxidation of CO in H 2 -rich gases (PROX) Project leader: Sebastian Lang Collaboration with ITTK (Prof. Türk) Funded by DFG Methanol to olefins Syngas to gasoline Project leader: Daniel Haigis Collaboration with ITC-TAB (Prof. Kolb) Funded by Start-Up Budget (KIT) Methanol to gasoline Project leader: Jens Adler Project leader: Markus Menges Funded by FNR and by ExxonMobile (4 years Collaboration with EBI (Prof. Schaub) Funded by FNR 9 Prof. Dr. B. Kraushaar-Czarnetzki
Fuels from Syngas Fischer-Tropsch (Sasol, BASF) TIGAS (Haldor-Topsoe) MTG (ExxonMobil) MTD (Lurgi) DTG Gasoline Syngas Methanol DME Olefins COD (Lurgi) MTO (UOP, Mobil) DTO MOGD (ExxonMobil) STD (Haldor-Topsoe, Air Products, JFE) MtSynfuels (Lurgi) Kero & Gasoil Fischer-Tropsch (Sasol, Shell) Paraffins 10 Prof. Dr. B. Kraushaar-Czarnetzki
Fuels from Syngas Fischer-Tropsch (Sasol, BASF) TIGAS (Haldor-Topsoe) MTG (ExxonMobil) MTD (Lurgi) DTG Gasoline Syngas Methanol DME Olefins MTO (UOP) DTO MOGD (ExxonMobil) STD (Haldor-Topsoe, Air Products, JFE) Kero & Gasoil MtSynfuels (Lurgi) Fischer-Tropsch (Sasol, Shell) Paraffins 11 Prof. Dr. B. Kraushaar-Czarnetzki
Formation of Methanol and DME (I) methanol synthesis CO + 2 H 2 CH 3 OH H θ = -92 kj/mol cat.: Cu/ZnO-based 60-80 bar 230-260 C DME synthesis 2 CH 3 OH DME + H 2 O H θ = -23 kj/mol cat.: γ-al 2 O 3 2-30 bar 200-250 C Gasoline Syngas Methanol DME Olefins combination easily possible because: Cu/ZnO also catalyses the shift reaction! Kero & Gasoil CO + H 2 O H 2 + CO 2 catalyst: Cu/ZnO/γ-Al 2 O 3 total: 3 H 2 + 3 CO DME + CO 2 12 Prof. Dr. B. Kraushaar-Czarnetzki
Formation of Methanol and DME (II) advantages of the combination: 4 H 2 + 2 CO 2 CH 3 OH 2 CH 3 OH DME + H 2 O CO + H 2 O H 2 + CO 2 total: 3 H 2 + 3 CO DME + CO 2 - MeOH equilibrium shifted due to DME formation - DME equilibrium shifted due to WGS reaction low H 2 /CO feed ratio possible (1:1) high conversion at low pressure feasible low recycle ratio feasible Equilibrium conversion vs. pressure (240 C; H 2 :CO:CO 2 = 51:48:1) N.R. Udengaard (Haldor Topsoe), Houston 2008 STD-processes: - Haldor Topsoe - Air products -JFE 13 Prof. Dr. B. Kraushaar-Czarnetzki
Olefins (I): Formation from MeOH/DME MTO (methanol to olefins) processes... include a 1st stage for separate DME formation 1st reactor: following reactor(s): 2 CH 3 OH DME + H 2 O DME/CH 3 OH C 2=, C 3=, HCs, H 2 O cat.: γ-al 2 O 3 cat.: ZSM-5 or SAPO 34 2-10 bar 2-10 bar 200-250 C 400-450 C Gasoline Syngas Methanol DME Olefins fixed bed: - Mobil Oil - Lurgi (MTP = methanol to propylene) fluidised bed (2nd stage): - Mobil Oil in cooperation with Uhde GmbH and Union Rheinische Braunkohlen Kraftstoff AG - UOP/Hydro (using SAPO-34 as a Katalysator) Kero & Gasoil 14 Prof. Dr. B. Kraushaar-Czarnetzki
Olefins (II): Conversion to Fuels Gasoline Syngas Methanol DME Olefins Kero & Gasoil Principle: acid-catalysed oligomerisation of light olefins Products: methyl-branched iso-olefins till C 20, hydrogenation required for distillates manufacturing Processes: - to gasoline from C 3 /C 4 -olefins: UOP CatCon (UOP Catalytic Condensation) - to gasoline and gasoil from FT-olefins: Lurgi COD (Lurgi Conversion of Olefins to Distillates) - to gasoline and middle distillates: MOGD (Mobil Olefin to Gasoline & Distillate) 15 Prof. Dr. B. Kraushaar-Czarnetzki
Olefins (III): Conversion to Fuels Daily spot prices of regular gasoline 2,2 $/gallon 660 $/ton gasoline? Olefins Gasoline Kero & Gasoil European ethylene and propylene closing prices Product August 3th, 2010 Unit www.eia.doe.gov ethylene 1000-1005 $/ton propylene 925-930 /ton www.lookchem.com 16 Prof. Dr. B. Kraushaar-Czarnetzki
Formation of Gasoline from MeOH/DME (I) Gasoline formation from MeOH/DME Gasoline Syngas Methanol DME Olefins...includes olefins as intermediates 2 CH 3 OH CH 3 OCH 3 + H 2 O HCpool* C 2 H 4 C 3 H 6 i-c 4 H 8 *HC-pool theory: Kolboe (1993) higher olefins aromatics paraffins coke 17 Prof. Dr. B. Kraushaar-Czarnetzki
Formation of Gasoline from MeOH/DME (II) Two processes for gasoline (both fixed bed): MTG (ExxonMobil Research and Engineering/Uhde) syngas MeOH MeOH DME gasoline Uhde: gasification & MeOH-synthesis TIGAS (Haldor Topsoe) syngas MeOH/DME gasoline 18 Prof. Dr. B. Kraushaar-Czarnetzki
Formation of Gasoline from MeOH/DME (III) Haldor Topsoe: TIGAS demo plant 8 b/d, Houston,TX ExxonMobil: MTG plants top: New Plymouth, 1985-1995, 14500 b/d left: Shanxi (China), since 2009, 2500 b/d 19 Prof. Dr. B. Kraushaar-Czarnetzki
Formation of Gasoline from MeOH/DME (IV) Similar product qualities have been reported by Haldor Topsoe for TIGAS Gasoline 20 Prof. Dr. B. Kraushaar-Czarnetzki
Chemistry of MTG and MTO 2 CH 3 OH CH 3 OCH 3 H + 2 O HCpool C 2 H 4 C 3 H 6 i-c 4 H 8 higher olefins aromatics paraffins (coke) T & p cracking! C 2 H 4 C 3 H 6 MTG processing mode T opt = 350 C p> 20bar (p opt =?) catalyst = ZSM-5 Si/Al Zeo = 30 MTO processing mode T opt = 450 C p opt = 2 bar catalyst = ZSM-5* ) Si/Al Zeo = 250 * ) fixed bed process in MTO, olefins occur as both: short-life intermediates and final cracking products 21 Prof. Dr. B. Kraushaar-Czarnetzki
Related Research at CVT till 2009: MTO only (propene & ethene are more valuable than fuels) development of a coke-resistant catalyst (runtime 3 months at high severity) processing and feedstock studies since 2009, funded by FNR (collaboration with Prof. Schaub, EBI): studies on the transition MTO/MTG improvement of the MTG-catalyst stability kinetic modelling development of reactor models identification of factors dominating total yields and efficiencies with respect to carbon and energy comparison of MtH-based and FT-based synfuel manufacturing 22 Prof. Dr. B. Kraushaar-Czarnetzki