Methanol Synthesis from Renewable Sources. John Bøgild Hansen - Haldor Topsøe PROMSUS Workshop, Gothenburg May 6, 2014

Transcription

1 Methanol Synthesis from Renewable Sources John Bøgild Hansen - Haldor Topsøe PROMSUS Workshop, Gothenburg May 6, 2014

2 We have been committed to catalytic process technology for more than 70 years Founded in 1940 by Dr. Haldor Topsøe Revenue: 700 million Euros 2700 employees Headquarters in Denmark Catalyst manufacture in Denmark and the USA

3 Topsoe Fuel Cell A/S Founded in 2004 after more than 20 years of research and development Located in Lyngby, Denmark (north of Copenhagen) Employees 105 Development, manufacturing and marketing of the Solid-Oxide Fuel Cell technology (SOFC technology) Subsidiary of Haldor Topsøe A/S (100%) Topsoe Fuel Cell Employees Headquarters in Lyngby, Denmark Supported by funding under the LIFE Programme of the European Union

4 Topsøe s position in methanol industry Number of plants: Accumulated capacity, MTPD: Number of catalyst charges: 1 1, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ,400 37

5 Market share

6 Methanol synthesis CO + 2H 2 = CH 3 OH + 91 kj/mol CO 2 + 3H 2 = CH 3 OH+H 2 O + 41 kj/mol

7 The Active Site of Syngas Catalyst H 2 H 2 /H 2 O Cu(200), d=0.18nm Cu(111), d=0.21nm Cu(111) Cu(111) Cu is metallic when catalyzing: - WGS - MeOH synthesis - MeOH reforming 1.5mbar, 220 o C ZnO(011), d=0.25nm ZnO(012), d=0.19nm 1.5mbar, H 2 /H 2 O=3/1, 220 o C Catalyst dynamic: - Number of active sites depends on conditions

8 FENCE technology Optimising sintering barriers Cu crystals separated by picket fence of metal oxides The FENCE technology inhibits sintering ZnO Cu Al 2 O 3

9 Catalyst activity Industrial experience benefits Increased loop efficiency Production gain Increased carbon efficiency Lower energy consumption Longer catalyst lifetime Less replacements Increased plant availability Statoil, Norway, 2500 MTPD 28.8 GJ/MT => 69 % effeiciency MK-151 FENCE MK % 20% MK-101 MK-151 FENCE Days on Stream MK-121 MK-101

10 Conversion of methanol as function of CO 2 content in stoichiometric gas Carbon conversion % J.B. Hansen Data Condensing methanol K.Klier Data Lab data 225 C Percent CO2 in

11 Ageing of methanol catalyst in Normal and Dry Syngas Relative activity /1-gas 40 5/5-gas Time on stream, hours

12 Reformers for Methanol Plant utilising CO 2 ¾CH 4 + ½H 2 O + ¼CO 2 = CH 3 OH

13 Methanol from sustainable sources BioDME Black Liqour to Green DME Demo CO2 Black Liq. AGR DME Unit WGS Sulphur Guard MeOH Synthesis Water

14 Wood to Gasoline DOE Project Green Gasoline from Wood Using Carbona Gasification and Topsoe TIGAS Processes

15 Fuel Cell and Electrolyser SOFC SOEC H 2 H 2 O H 2 O H 2 H 2 + O 2- H 2 O + 2e - O 2- ½O 2 + 2e - O 2- H 2 O + 2e - H 2 + O 2- O 2- O 2-2e - +½O 2 ½O 2 ½O 2 H 2 + CO + O 2 SOF C SOEC H 2 O + CO 2 + electric energy ( G) + heat (T S)

16 GreenSynFuel Project

17 Mass Flows in Wood to MeOH

18 Mass Flows in Wood + SOEC to MeOH

19 Effciencies: Stand alone wood gasifier and gasifier plus SOEC LHV Efficiency % Wood Gasifier alone Wood gasifier Plus SOEC Methanol District Heat Total

20 Methanol from CO 2 and Steam SOEC Water P 1 E 1 E 3 E 4 Oxygen K 1 E 6 K 2 CO2 Recycle K 3 Methanol Reactor Purge E 7 Methanol

21 Synergy between SOEC and fuel synthesis Product CO 2 SOEC Syn Gas Synthesis H 2 O Steam

22 Reactor Volume Relative % Reactor volume and byproducts as function of CO 2 converted in SOEC Byproducts Relative % Reactor Volume Byproducts Percent CO 2 through SOEC

23 Results of to pressurize SOEC stacks or not SOEC Pressure Syngas Comp % CO2 Comp LHV Efficiency % Atmospheric bar Max. theoretical 83-88

24 Conclusions Very efficient methanol plants based on power, steam and CO 2 is possible via SOEC Co-electrolysis offers the opportunity to reduce methanol synthesis catalyst volumes by a factor around 5 Pressurising the SOEC stacks can eliminate synthesis gas compressor and increase efficiency Coupling SOEC with biomass gasification can double the biomass potential by converting excess carbon.

25 The CO 2 Electrofuel Project CHEMREC Energy to Succeed Is CO 2 electrofuels a viable and competitive technology for the Nordic countries?

26 SOEC more efficient than present Electrolysers Internal waste heat used to split water kwh per Nm3 H Energy needed to evaporate water Waste heat which can be utilised to split water Minimum Electricity Input Deg C.