(Syn)Gas to Fuel HIGH QUALITY GASOLINE FROM METHANOL

(Syn)Gas to Fuel HIGH QUALITY GASOLINE FROM METHANOL Public N. Ringer/ R. Rakoczy Business Unit Catalysts 09.09.2013 2 Agenda Introduction MTG: History & Chemistry The Catalysts CAC s STF Process Conclusions

Introduction Public N. Ringer/ R. Rakoczy Business Unit Catalysis and Energy 09.09.2013 A Lot Goes on in the Methanol Industry Breakthrough in on-purpose Propylene / Olefins from Methanol: successful start-up and operation of MTP / MTO plants in China Methanol has arrived in the energy sector: Blending into Gasoline is reality in China Feedstock: basically Coal in China and NG elsewhere Now: Shale gas heralds a new era in North America!

Shale Gas Heralds New Era*) US shale gas production as a game changer in the US gas market which h is now no longer in decline; Gas is now available in abundance and can be produced at relatively low cost; Price is steeply down from 12 $/MM BTU not long ago to ca. 4 $/MM BTU now; Shale gas revolution could lead to a major change in the chemical industry: => Gas to Chemicals and Gas - to - Fuels! *) ICIS Chemical Business, Issue January 16-22, 2012 6 Synthetic Fuels - Alternative Route to Energy Carbonaceous source Fuel Natural gas Crude oil associates gas Partial non catalytic oxidation Shale gas Biomass Residues Catalytic auto thermal reforming Syngas to methanol Methanol to fuel GA ASOLINE Coal Gasification

MTG History & Chemistry Public N. Ringer/ R. Rakoczy Business Unit Catalysis and Energy 09.09.2013 8 Methanol to Gasoline - Commercialization Developed in 1970 by Mobil Catalyst based on zeolite ZSM-5 (MFI topology) Process set-up with catalytic DME pre-reactor and catalytic gasoline reactor Adiabatic pre-reactor inlet 280-320 C, gasoline reactor 400-420 C Operation close to ambient pressure Product carbon content maximum C10 Commercialization Oct. 1985 in METHANEX methanol plant in New Zealand Unit shut down in 1998 Source: John Packer, P. Kooy, C M Kirk, Clare Wrinkes, The production of methanol to gasoline, http://nzic.org.nz/chemprocesses/energy/7d.pdf

9 Methanol to Gasoline - Process and Product Issues Highly exothermic 1740kJ heat per kg of methanol converted Heat removal as inherent issue (pre-reactor and gasoline reactor) Coke formation rate calls for a set of reactors Significant amounts of traces of methanol in water out of the process High formation of 3-6%-wt. of 1,2,4,5 tetra-methyl-benzene (durene) is problematic Source: John Packer, P. Kooy, C M Kirk, Clare Wrinkes, The production of methanol to gasoline, http://nzic.org.nz/chemprocesses/energy/7d.pdf 10 Durenes - Evaporation issue 1,2,4,5 tetramethylbenzene 1,2,3,5 tetramethylbenzene m.p. 79 C m.p. -24 C The high melting point of 1,2,4,5 tetramethylbenzene causes carburator icing Source: John Packer, P. Kooy, C M Kirk, Clare Wrinkes, The production of methanol to gasoline, http://nzic.org.nz/chemprocesses/energy/7d.pdf

11 Methanol to Gasoline - Chemistry SELECTIVIT Y in %-wt. SPACE TIME in HOURS Source: John Packer, P. Kooy, C M Kirk, Clare Wrinkes, The production of methanol to gasoline, http://nzic.org.nz/chemprocesses/energy/7d.pdf 12 Methanol to Gasoline - Product Hydrocarbon product content in %-wt. C 1,C 2 1.4 C 3 5.5 C = 3 0.2 i C 4 8.6 n C 4 33 3.3 C = 4 1.1 C 5+ hydrocarbons 79.9 Source: John Packer, P. Kooy, C M Kirk, Clare Wrinkes, The production of methanol to gasoline, http://nzic.org.nz/chemprocesses/energy/7d.pdf

13 Methanol to Gasoline - Product Gasoline composition content in %-wt. Highly branched alkanes 53 Highly branched alkenes 12 Naphthenes 7 Aromatics 28 Source: John Packer, P. Kooy, C M Kirk, Clare Wrinkes, The production of methanol to gasoline, http://nzic.org.nz/chemprocesses/energy/7d.pdf The Catalysts Public N. Ringer/ R. Rakoczy Business Unit Catalysis and Energy 09.09.2013

15 CLARIANT Catalysts for Synthetic Fuel Production COD - 900 Catalyst for the conversion of light olefins to distillates CPA - 100 Catalyst for conversion of paraffins to gasoline (ZEOFORMING) DME - 100 Catalyst for conversion of methanol to dimethylether CMG - 100 Catalyst for conversion of methanol to gasoline (first generation) SMA-2 Catalyst for gasoline production from methanol tailored for STF process by CAC FTMax - Series Catalyst products for Fischer-Tropsch synthesis 16 CLARIANT Catalysts for Synthetic Fuel Production COD - 900 Catalyst for the conversion of light olefins to distillates CPA - 100 Catalyst for conversion of paraffins to gasoline (ZEOFORMING) DME - 100 Catalyst for conversion of methanol to dimethylether CMG - 100 Catalyst for conversion of methanol to gasoline (first generation) SMA-2 Catalyst for gasoline production from methanol tailored for STF process by CAC FTMax - Series Catalyst products for Fischer-Tropsch synthesis

17 CLARIANT s Experience in Conversion of Methanol CMG - 100 Zeolite MFI (ZSM-5) based catalyst Optimized hydrothermal stability Easy to install High Methanol conversion rate Easy to regenerate Low Durene make, less work-up requirement Patented in 1998 Evaluated and approved at the METHANEX MTG Plant in Plymouth, New Zealand 18 CMG-100 Chemistry MeOH molecules flow into a Reactor filled with CMG-100 Catalyst.... inside the pores of the CMG-100 catalyst carbon atoms join up in complex strings with hydrogen to form hydrocarbons (Gasoline). The zeolitic CMG-100 catalyst causes MeOH to rearrange. Two hydrogen atoms join onto one oxygen atom to form water while...

19 CMG-100 Commercially Proven CMG-100 STF The Technology Public N. Ringer/ R. Rakoczy Business Unit Catalysis and Energy 09.09.2013

21 STF Process Concept by Chemieanlagenbau Chemnitz 22 STF Process - Unique advantages (I) easy and optimal process control high product yield and product selectivity with lowest unwanted by-products levels due to -isothermal reaction process -optimized recycling of non-used components -isothermal reactors allowing stable process control and optimal reaction conditions -tailor-made SMA-2 catalyst by CLARIANT substantial reduction of the recycling gas quantity due to use of isothermal reactors compared to adiabatic reactors

16th IMPCA 2013 Asian Methanol Conference 23 STF Process - Unique Advantages (II) increase of catalyst lifetime and cycle length of the synthesis catalyst due to isothermal reaction process use of the reaction heat of the exothermic gasoline synthesis for HP steam generation use of the generated steam as energy source in the process and for generation of electrical energy process water is fully cleaned of methanol and other oxygenated components a biological purification of waste water is not required product gasoline complies DIN EN 228 and European emission standard EURO 5 and does not require any further refining 24 STF Process - Demonstration Plant

25 STF Process - Gasoline Properties STF fuel DIN EN 228:2004-03 gasoline, regular Density (15 C) 750 760 720 775 kg/m³ Molecular mass 95 96 kg/kmol Paraffins 30 40 %-wt. Olefins 4 6 max. 18 %-wt. Naphthenes 7 9 %-wt. Aromatic compounds 34 36 max. 35 %-wt. Benzene 0,2 0,4 max. 1 %-vol. Durene 1245Trimethylbenzene 1,2,4,5-Trimethylbenzene max. 3 %-vol. Research octane number 93 95 min. 91 Motor octane number 84 85 min. 82,5 Vapor pressure 66,7 max. 100 kpa Boiling range 40 186 - C 26 STF Gasoline - Applicability tests First results of full load mode: tests with a modern fuel injection motor (Downsizing Concept) Comparative fuel: Gasoline RON 95 ( Super E10 with 5.1% Ethanol) p [bar] me 26 24 22 20 18 16 14 12 STF Benzin Charge 2 Basis Benzin ROZ95 16 Valuation of Results: With STF gasoline nearly same results under full load at constant charging pressure Ignition angle with STF gasoline minimal later (ca. 1 KW), this means knocking behavior slightly higher Specific fuel demand Beff until 4000 1/min for both fuels identical, at higher speed (number of revolutions) slightly higher Beff [g/kwh] 400 375 350 325 300 275 12 8 4 0-4 -8-12 Ignition Zündwinkel Angle [-] [-] 250 1000 2000 3000 4000 5000 6000 Drehzahl Speed [1/min] in cooperation with:

27 STF commercial scale plant - Capacities Balance for 50.000 t/a final product gasoline plant capacity Raw material Products t/a kg/h % t/a kg/h % methanol water 134.991 14.999 16.070 1.786 90 10 gasoline fuel gas LPG heavy gasoline water 50.000 5.373 2.489 1.197 90.931 5.952 640 296 143 10.825 33,3 3,6 1,7 0,8 60,6 149.990 17.856 100 149.990 17.856 100 electrical energy excess 2,4 MW Conclusions Public N. Ringer/ R. Rakoczy Business Unit Catalysis and Energy 09.09.2013

29 (Syn)Gas to Fuel - Summary A new process for the production of high-octane gasoline from methanol has been developed. The essential targets t in the process development have been: Achievement of high product yields and selectivity at low capital and energy costs. Generation of a product, which does not need further refining but is in compliance with a highoctane gasoline as per DIN EN 228 standard. Development of an almost effluent free technology PLANT CAPACITY: 50.000000 t/a product gasoline Based on SMA-2 catalyst made by Clariant THANK YOU FOR YOUR KIND ATTENTION! Public N. Ringer/ R. Rakoczy Business Unit Catalysts 09.09.2013