The Methanol Synthesis past and future. John Bøgild Hansen - Haldor Topsøe International Methanol Conference Taastrup May 10, 2017

Transcription

1 The Methanol Synthesis past and future John Bøgild Hansen - Haldor Topsøe International Methanol Conference Taastrup May 10, 2017

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, China and the USA 2

3 Topsøe methanol technology and catalyst milestones SMK CMD revamp concept MK-121 MK-151 FENCE 1st methanol plant MK-101 Two step reforming World scale plant 2 * 5000 MTPD scale plant

4 Topsoe methanol plants Since 2000 Number of plants: 40 Accumulated capacity, MTPD: 97,075 Number of catalyst charges:

5 Methanol market share Awarded capacity Chinese Lic. 4% Others 14% HTAS 28% Casale 13% Lurgi 15% Davy 26% 5

6 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 6

7 Catalyst activity Industrial benefits Industrial experience 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 % efficiency MK-151 FENCE MK % 20% MK-101MK-151 FENCE Days on Stream MK-121 MK-101 7

8 Reformers for Methanol Plant utilising CO 2 ¾CH 4 + ½H 2 O + ¼CO 2 = CH 3 OH 8

9 Methanol from sustainable sources BioDME Black Liqour to Green DME Demo CO2 Black Liq. AGR DME Unit WGS 9 Sulphur Guard MeOH Synthesis Water

10 Wood to Gasoline DOE Project Green Gasoline from Wood Using Carbona Gasification and Topsoe TIGAS Processes 10

11 The Active Site of Syngas Catalyst Cu(200), d=0.18nm Cu(111), d=0.21nm H 2 Cu(111) H 2 /H 2 O Cu(111) Cu is metallic when catalyzing WGS MeOH synthesis MeOHreforming ZnO(011), d=0.25nm ZnO(012), d=0.19nm Catalyst dynamic Number of active sites depends on conditions 1.5mbar, 220 o C 1.5mbar, H 2 /H 2 O=3/1, 220 o C 11

12 Conversion of methanol as function of CO 2 content in stoichiometric gas 100 Carbon conversion % J.B. Hansen Data Condensing methanol K.Klier Data Lab data 225 C Percent CO2 in 12

13 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 13 SOFC SOEC H 2 O + CO 2 + electric energy ( G) + heat (T S)

14 Separator Methanol synthesis Methanol From CO 2 and Steam SOEC Oxygen Water CO 2 Recycle Purge Methanol 14

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

16 Synergy between SOEC and fuel synthesis Effciencies electricity to MeOH = % possible CO 2 SOEC Syngas Synthesis Product H 2 O Steam 16

17 EUDP project 50 kw SOEC and 10 Nm 3 /h methane Participants: Haldor Topsøe A/S Aarhus University HMN Naturgas Naturgas Fyn EnergiMidt Xergi DGC PlanEnergi Ea Energianalyse Coordinator: Duration: June September 2017 Project sum: 5.3 mio Location: Foulum 17

18 Methanation and SOEC at Foulum 18

19 Percent of Design production Operating Temp C Production vs hours on stream. 3.1 kwh/nm 3 H 2 120% % % % % % % Hours on Electrolysis

20 Deg. Celcius Results from Foulum Methanator Temperature profile in Methanator ,5 1 1,5 2 2,5 3 Meters from catalyst inlet 20

21 Average gas compositions Position CH 4 CO 2 N 2 H 2 Biogas Exit 1 st stage Product gas

22 GreenSynFuel Project 22

23 Mass Flows in Wood to MeOH 1000 tons Wood 704 tons CO tons Oxygen 59 % LHV efficiency 523 tons MeOH 23

24 Mass Flows in Wood + SOEC to MeOH 1000 tons Wood 782 tons Oxygen 262 tons Oxygen 1053 tons MeOH 141 MW electricity 71 % LHV efficiency 24

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

26 Conclusions Haldor Topsøe is a major player within the methanol industry CO 2 is already today used to enhance methanol production based on natural gas steam reforming 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 Coupling SOEC with biomass gasification can double the biomass potential by converting excess carbon. 26

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