Methanol Production Technology: Todays and future ...

1 John B gild Hansen - Haldor Tops e Methanol Workshop, Lund University March 17, 2015 Methanol Production technology : Todays and future Renewable Solutions We have been committed to catalytic process technology for more than 70 years Founded in 1940 by Dr. Haldor Tops e Revenue: 700 million Euros 2800 employees Headquarters in Denmark Catalyst manufacture in Denmark and the USA Tops e s position in Methanol industry Number of plants: Accumulated capacity, MTPD: Number of catalyst charges: 1 1,650 1 1 3,300 2 2 4,950 2 3 6,600 3 4 8,250 3 4 9,900 5 5 11,550 6 6 13,200 7 8 14,850 6 9 16,500 7 10 18,150 7 15 19,800 12 16 21,450 12 17 23,100 13 18 24,750 13 19 26,400 14 20 28,050 14 20 29,700 15 21 31,350 15 22 33,000 16 23 34,650 17 24 36,300 17 25 37,950 18 26 39,600 18 27 41,250 19 28 42,900 20 29 44,550 20 30 46,200 21 31 47,850 22 32 49,500 22 33 51,150 23 34 52,800 24 35 54,450 24 36 56,100 25 37 57,750 25 38 59,400 26 39 61,050 26 40 62,700 27 41 64,350 28 42 66,000 28 42 67,650 29 43 69,300 30 44 70,950 30 44 72,600 31 45 74,250 32 46 75,900 33 47 77,550 33 47 79,200 34 48 80,850 34 48 82,500 35 49 84,150 35 50 85,800 36 51 87,450 36 52 89,100 37 53 90,750 37 54 92.

2 400 37 Methanol synthesis CO + 2H2 = CH3OH + 91 kJ/mol CO2 + 3H2 = CH3OH+H2O + 41 kJ/mol Tops e technologies for shale gas based Methanol plants Tubular reforming Two-step reforming Reforming technologies Synthesis technologies Distillation technologies Boiling water reactor Single column 2 columns 3 columns Natural gas Autothermal reforming Adiabatic reactors Grade AA Fuel grade Steam Steam Makeup comp. Methanol reactor Raw Methanol Condensate Steam reformer Sulphur remov. Sulphur removal Natural gas Prereformer Methanol Production by one-step reforming Steam Pre- reformer Secondary reformer Steam Steam Oxygen Makeup comp. Light ends to fuel Methanol reactor Water Raw Methanol Raw Methanol storage Condensate Steam reformer Sulphur sat. removal Hydrogenator Natural gas Product Methanol Methanol Production by two-step reforming Economy of scale H2O/CH4 Air H2O/CH4 O2 Syngas Air H2O/CH4 O2 Syngas Log capacity Log costs Tubular Reforming O2-plant Photo: yvind Hagen, Statoil Tubular reformer for Methanol plant based on two-step reforming Tops e boiling water cooled Methanol reactors at Bandar Imam, Iran Methanol Production by ATR Oxygen/steam Steam Steam Raw Methanol Natural gas Water Condensate Purge gas Hydrogen recovery Methanol reactor Autothermal reformer Hydro- genator Sulphur removal Saturator Pre- reformer Makeup comp.

3 Rec. comp. Tops e ATR reactor Large single line capacity Economic of scale Soot-free process In industrial operation Low steam to carbon (S/C < ) Oxygen Hydrocarbon + steam CTS burner Synthesis gas Combustion zone Catalyst Pressure shell Refractory Projects using ATR for synthesis gas generation Oryx, Qatar (GTL) 34,000 BPD Escravos, Nigeria (GTL) 34,000 BPD Viva, Nigeria ( Methanol ) 10,000 MTPD Sasolburg, South Africa (syngas) 2 x 215,000 Nm3/h Increased loop efficiency Production gain Increased carbon efficiency Lower energy consumption Longer catalyst lifetime Less replacements Increased plant availability Industrial experience Days on Stream Catalyst activity MK-151 FENCE MK-121 MK-101 20% 20% MK-151 FENCE MK-121 MK-101 Statoil, Norway, 2500 MTPD GJ/MT => 69 % effeiciency Industrial benefits Reformers for Methanol Plant utilising CO2 CH4 + H2O + CO2 = CH3OH Fuel Cell and Electrolyser O2 H2 H2O O2 H2O + 2e- H2 + O2- O2- O2- 2e- + O2 H2 + O2- H2O + 2e- O2- O2 + 2e- O2- SOFC SOEC H2 H2O H2 + CO + O2 H2O + CO2 + electric energy ( G) + heat (T S) SOFC SOEC Cu(111), d= Cu(200), d= ZnO(011), d= ZnO(012), d= Cu(111) Cu(111) H2 H2/H2O , 220oC , H2/H2O=3/1, 220oC The Active Site of Syngas Catalyst Cu is metallic when catalyzing.

4 - WGS - MeOH synthesis - MeOH reforming Catalyst dynamic: - Number of active sites depends on conditions Conversion of Methanol as function of CO2 content in stoichiometric gas 0102030405060708090100051015202530 Percent CO2 in Carbon conversion % Hansen Data Condensing Data Lab data 225 CAgeing of Methanol catalyst in Normal and Dry Syngas 120 80 40 0 0 200 400 600 800 Time on stream, hours Relative activity 10/1-gas 5/5-gas Methanol from CO2 and Steam P 1 SOECP urgeWaterE 3E 6E 7E 4E 1CO2 MethanolMethanolReactorK 2K 1K 3 RecycleOxygenSynergy between SOEC and fuel synthesis SOEC Synthesis CO2 H2O Syn Gas Product Steam Reactor volume and byproducts as function of CO2 converted in SOEC 0300600900120001002003004005006007000204 06080100 Byproducts Relative % Reactor Volume Relative % Percent CO2 through SOEC Byproducts Reactor Volume Methanol from sustainable sources BioDME Black Liqour to Green DME Demo CO2 Black Liq.

5 Water WGS Sulphur Guard MeOH Synthesis AGR DME Unit GreenSynFuel Project Mass Flows in Wood to MeOH Mass Flows in Wood + SOEC to MeOH Effciencies: Stand alone wood gasifier and gasifier plus SOEC LHV Efficiency % Wood Gasifier alone Wood gasifier Plus SOEC Methanol District Heat Total The CO2 Electrofuel Project CHEMREC Energy to Succeed Is CO2 electrofuels a viable and competitive technology for the Nordic countries?