Fuels from Renewable Sources John Bøgild Hansen - Haldor Topsøe
Thermochemical pathways Biomass Other HC feed Gasification Tar Reforming CO 2 removal FT SNG Hydro Cracking Tigas Natural Gas Diesel DOE Tigas Qinghua GobiGas Qinghua Gasoline Natural Gas Syngas reforming MeOH MeOH GTL plants Small scale GTL plants DME DME MeOH plants Piteå
Tar reforming Enabling technology for biomass gasification Gasification of biomass results in a syngas that contains tars and contaminants 1000-2500 ppm tar 50 100 ppm S, particulates 850-930 C, 1-30 bar g Ammonia decomposition BIOMASS GASIFIER TAR REFORMER ASH
Clean tar reforming QUENCH GAS HIGH TEMPERATURE HOT GAS FILTER Clean tar reforming 1-10 mg dust / Nm 3 BIOMASS -FEED DUST GASI FIER TAR REFOR MER ASH PROCESSING & UTILIZATION
Dusty tar reforming BIOMASS -FEED GASI FIER TAR REFOR MER Dusty tar reforming 10-30 g dust / Nm 3 HOT GAS FILTER ASH PROCESSING & UTILIZATION
Skive Fjernvarme a.m.b.a. (Skive CHP) Location Capacity Skive, Denmark 21 MW th, Max 28 MW th Operational year 2009 Fuel consumption Fuel Gasification techn. Pressure range Power source 100 MTPD Biomass, wood pellets Air blown, bubbling fluidized bed Atmospheric to medium Gas engines
Skive Fjernvarme a.m.b.a. (Skive CHP)
GTI Chicago Location Capacity Fuel consumption Fuel Gasification techn. Pressure range Chicago, USA ~ 4 MW th 18 MTPD Biomass, wood pellets Oxygen blown, bubbling fluidized bed 1-9 bar g
Gas Technology Institute, Chicago Tar reformer ~ 1150 run hrs No soot formation 750 950 C 1050 1375 Nm 3 /h 30 160 ppmv H 2 S 15 min. lack of oxygen No deactivation! Full tar conversion
Sidestream pilot collaboration with DTI 790 C 5 Nm 3 /h 40 ppmv H 2 S At Skive CHP for ~ 600 hrs Movable unit Specified tar conversion of: ~ 80 % Naphthalene, ~ 55 % Benzene ~ 80 % Toluene
Clean and Dusty tar reforming Key points Versatile knowledge and practical know-how Clean tar reforming: SNG and BtL designs Dusty tar reforming: CHP and SNG designs On-site sidestream pilot
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
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)
SOEC more efficient than present Electrolysers Internal waste heat used to split water 4.0 3.5 Energy needed to evaporate water kwh per Nm3 H2 3.0 2.5 2.0 1.5 1.0 Waste heat which can be utilised to split water Minimum Electricity Input 0.5 0.0 0 100 200 300 400 500 600 700 800 900 1000 Deg C.
Electrolysis Power Steam CO 2 CO CO 2 H 2 Syngas Hydrogen SNG Methanol DME Gasoline Diesel
Topsøe TREMP Methanation proces
SNG Technology Methanation generates a lot of heat CO 2 + 4H 2 CH 4 + 2H 2 O (- H = 165 kj/mol) Syngas = SNG + heat Energy: 100% = 80% + 20% Heat 20% 100% SNG 80%
Biogas upgrade by means of SOEC ForskNG Project 10677 CH 4 + CO 2 + 3H 2 O + El 2CH 4 +H 2 O + 2O 2 Participants: Haldor Topsøe A/S Ea Energianalyse Risø DTU Topsoe Fuel Cell A/S ForskNG Support 911 kkr. Q2 2011 Q1 2012
Biogas to SNG via SOEC and methanation of the CO 2 in the biogas:
Exergy Flows in CO 2 case
New EUDP project 40 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 Cemtec Coordinator: Duration: June 2013 - July 2016 Project sum: 5.3 mio Location: Foulum
Methanol synthesis CO + 2H 2 = CH 3 OH + 91 kj/mol CO 2 + 3H 2 = CH 3 OH+H 2 O + 41 kj/mol
Conversion of methanol as function of CO 2 content in stoichiometric gas 100 Carbon conversion % 90 80 70 60 50 40 30 20 10 0 J.B. Hansen Data Condensing methanol K.Klier Data Lab data 225 C 0 5 10 15 20 25 30 Percent CO2 in
Ageing of methanol catalyst in Normal and Dry Syngas 120 Relative activity 80 40 10/1-gas 5/5-gas 0 0 200 400 600 800 Time on stream, hours
GreenSynFuel Project
Mass Flows in Wood to MeOH
Mass Flows in Wood + SOEC to MeOH
Methanol from CO 2 and Steam
Effciencies: Stand alone wood gasifier and gasifier plus SOEC LHV Efficiency % Wood Gasifier alone Wood gasifier Plus SOEC Methanol 59.2 70.8 District Heat 22.6 10.8 Total 81.8 81.6
Synergy between SOEC and fuel synthesis Product CO 2 SOEC Syn Gas Synthesis H 2 O Steam
DME the versatile fuel TIGAS
Syngas to MeOH/DME Equilibrium 100 MeOH / DME 80 Conversion (H 2 +CO) 60 40 20 0 0 20 40 60 80 100 Pressure (bar g) MeOH T = 250 C H 2 = 51 CO = 48 CO 2 = 1 Equilibrium, mol% 100% 80% 60% 40% 20% Optimum ratio at H 2 :CO 1 CO DME CO 2 H 2 0% 0.5 1 1.5 2 2.5 H 2 /CO MeOH H 2 O
The first DME powered vehicle: Svend Erik Mikkelsens Lawn Mover
The second DME powered vehicle: LPG fork lift in the company LPG Fork Lift - used for Initial Studies of DME as Fuel
Methanol from sustainable sources BioDME Black Liqour to Green DME Demo Black Liq. CO 2 AGR DME Unit WGS Sulphur Guard MeOH Synthesis Water
DME - The ultimate compression Ignition/Diesel fuel Completely SOOTLESS (No smoke) 90% NOx reduction No sulphur Low HC, CO Meets/exceeds 2007 emission standards Quiet combustion High cetane Engine/fuel system lower cost than conventional diesel Fuel Distribution: Like LPG Pictures courtesy of Volvo Truck Corp and NKK Corp. Particulate (g/bhp-hr) Heavy-duty emissions estimates 0.08 Diesel 0.06 0.04 0.02 0.00 '01 DME '95 DME 0 1 2 3 4 NOx (g/bhp-hr)
TIGAS MTG Topsøe Integrated Methanol To Gasoline Synthesis Synthesis Gas Methanol Synthesis Day Tank (Raw Methanol) MeOH/DME Synthesis C 3 -C 4 MeOH DME Gasoline Synthesis Separation Gasoline Water
TIGAS - Historic Perspective 8 bpd Demonstration Facility (Houston, TX) lb/h Test Facility (Denmark) Current MTG Test Facility (Denmark)
25 bbl/d Demonstration Plant Green Gasoline from Wood Using Carbona Gasification and Topsoe TIGAS Processes BIOMASS BIOMASS GASIFIER TAR REFORMER TAR REFORMER GASIFIER OXYGEN Gas Cleaning MeOH /DME MeOH/DME Gasoline http://www.energy.gov/news2009/releases.htm ASH OXYGEN
Lab and Pilot Visit Three groups Places to visit: Motor Lab TIGAS and SNG Pilot Bench scale and characterisation labs