Fraunhofer UMSICHT»New Products made of Synthesis Gas derived from Biomass«3-6 May 2010 Presentation at Freiberg Conference on IGCC & XtL Technologies, Dresden Dipl.-Ing. Kai Girod Folie 1
Outline 1. Introduction of the Products 2. Synthesis of Products 3. Future Challenges 4. Future Work Folie 2
New Products made of Synthesis Gas derived from Biomass gaseous fuel (motor, turbine) state of the art synthetic natural gas (SNG) test stage Biomass- Gasification Synthesis Gas Fischer-Tropsch-Fuel Methanol pilot phase test stage/ pilot phase Ethanol new! Dimethylether (DME) new! The Fischer-Tropsch-Synthesis is performed in the pilot plant of Choren in Freiberg, Saxony The methane synthesis is in test stage (wood-gasifier-güssing, Austria) - 2 nd Generation Biogas - promising technology Direct utilisation of synthesis gas as fuel gas (power generation) is currently under operation around the world methanol is produced from gasified black liquor - pilot phase methanol from syngas is considered as feedstock for MTG-Process Folie 3
Bio-SynGas to Dimethyl Ether (DME) and Ethanol DME is a substitute for Diesel or LPG - more efficient land use compared to Bio-Diesel (FAME) - no competition on food and energy large scale production from natural gas or coal >10 Mio. t/a Our aim is the development of improved catalysts that can be adapted to existing biomass gasification processes Currently there are no commercial catalysts for ethanol synthesis from synthesis gas available Our aim is to develop new catalysts and a tailor-made process for Ethanol production from Bio-Syngas Chance: New perspectives for sustainable fuels - Petrol- and Diesel- Substitutes Folie 4
Reactions with Synthesis Gas H 2 /CO Methane CO + 3 H 2 CH 4 + H 2 O (3:1) Fischer-Tropsch-Synthesis n CO + 2n H 2 (-CH 2 -) n + n H 2 O (2:1) Methanol CO + 2 H 2 CH 3 OH (2:1) Ethanol 2 CO + 4 H 2 C 2 H 5 OH + H 2 O (2:1) Dimethylether 2 CO + 4 H 2 H 3 C-O-CH 3 +H 2 O (2:1) Methane (dry route) 2 CO + 2 H 2 CH 4 + CO 2 (1:1) Ethanol (dry route) 3 CO + 3 H 2 C 2 H 5 OH + CO 2 (1:1) Dimethylether (dry route) 3 CO + 3 H 2 H 3 C-O-CH 3 + CO 2 (1:1) Focus on syn-gas H 2 /CO ratio of one: higher syn-gas conversion main coproduct CO 2, separation is easier compared to water available wood-gasifier (autotherm) technology (Chrisgas, Carbo V, CUTEC) Folie 5
Two-Step Synthesis DME - Synthesis Methanol Synthesis CO + 2 H 2 CH 3 OH Methanol Dehydration 2 CH 3 OH CH 3 OCH 3 + H 2 0 One-Step Synthesis Direct Synthesis in one Reactor 3 CO + 3 H 2 CH 3 OCH 3 + CO 2 Synergetic Effects more beneficial state of equilibrium, higher DME yield Fixed Bed or Slurry Reactor, Catalyst Mixture of: Cu-ZnO-Al 2 O 3 (standard methanol synthesis catalyst, 80 %) γ-al 2 O 3 (Dehydration catalyst, 20 %) Reaction Conditions Temperature: 250 C Pressure: 5 MPa Typical Efficiency: 50% of Equilibrium CO-Conversion for Single-Pass-Process Folie 6
Evaluation of two Production Concepts concept1 allothermal athmospheric gasification (Taylor Biomass Energy) steam-blown, H 2 /CO=2.5 60 MW (12 t/h Wood daf) concept 2 autothermal, pressurized gasification (Värnamo Gasifier, Chrisgas Project) O 2 -blown, H 2 /CO=1 60 MW (12 t/h Wood daf) Folie 7
Production Concepts - Efficiency Efficiency 100% 90% 80% 70% 60% 50% 40% 30% 20% 10% Revenues [ 1,000 2008 ] 20,000 16,000 12,000 8,000 4,000 0% Concept 1 Concept 2 0 Concept 1 Concept 2 DME Electricity District heating Input: 60 MW (12 t/h Wood daf) Overall Efficiency Concept 1: 76.5% (of 67.3 MW) Concept 2: 73.8% (of 65.6 MW) Revenues: electricity district heating DME Electricity is most important DME revenues are less important only valid for given boundary conditions national subsidies Folie 8
Ethanol from Bio-Syngas advantages: complete utilisation of biomass utilisation of biomass residuals (straw, sewage sludge etc.) process scheme Biomassgasification gas treatment compression synthesis gasification + gas treatment (C 10 H 14 O 7 ) 6n + 20n O 2 40n CO + 40n H 2 + 20n CO 2 + 2 H 2 O Synthesis: 3 CO + 3 H 2 CH 3 -CH 2 -OH + CO 2 (ΔH R0-297 kj/mol) 2 CO + 4 H 2 CH 3 -CH 2 -OH + H 2 O (ΔH R0-256 kj/mol) Folie 9
Ethanol Energy Efficiency 100 % 59 % 29 % 46 % LCB O 2 - gasification 19 % LCBfermentation (state of the art) LCBfermentation (theoretically) LCB biomasse dry basis 12% Biomass demand for self-sufficient O 2 /pressure-supply (η el =0.35) 10% of Biomass is exported as electricity Folie 10
Ethanol Synthesis 3 H 2 + 3 CO CH 3 -CH 2 -OH + CO 2 H 2 /CO = 1 suppresses formation of Methanol compared to H 2 /CO = 2 Reaction conditions: T 275 ºC, p 10 MPa Heterogenous catalysis, catalyst type: - modified Rh-supported Rh-catalyst - modified Cu/Co/ZnO -MoS 2 1-2% CO 2 and N 2 do not interfere expected selectivity 75% Space Time Yield = 320 kg Ethanol/m 3 catalyst h catalysts are on test stage no fully developed catalysts on the market Folie 11
Future Challenges of BioSyngas Conversion technical: gas cleaning requirements: tar, S, Cl, N 2, CO 2 selection of catalysts reduction of pressure level (great influence on economic efficency) improvement of selectivity Catalyst development: various publications deal with new synthesis gas conversion catalysts most published experiments are performed in small batch reactors influence of minor components is unclear economical: minimum scale of a plant biomass logistics Folie 12
Future Work - Future Development A continuous test facility in laboratory scale is under constuction: Different heterogenous catalysts can be tested in different kinds of reactors (e. g. fixed bed, slurry) Reaction conditions can be varied pressure up to 10 MPa, Temperature up to 450 C variable mixtures of H 2, CO, CO 2, Ar adjustable recycle stream continuous product separation (condensation of DME, Ethanol, CO 2 ) online analysis of gas streams (IR) Analysis of liquid products in the laboratory Folie 13
Flow Scheme of the Laboratory Scale Test Facility H2, CO;CO2 online Analysis FIC Reactor 1 Reactor 2 Folie 14
Future Key Activities catalyst development close cooperation to Universities and plant engineering companies optimization of conversion rate and product selectivity optimized interaction of different reaction steps beneficial effect on the state of reaction equilibrium adaption of the catalytic process to basic conditions of the biomass gasification process reduction of the pressure level influence of minor components: Cl, S, Tar, NH 3, HCN evaluation of a large scale process Catalyst-/Process development is as an iterative procedure filling a gap in the field of catalyst research for SynGas Conversion Folie 15
Thank you for your Attention! Feel free to ask Questions Folie 16
Influence of Biomass Price on Production Costs 1,6 1,4 1,2 Ethanol cost price [ /l] 1 0,8 0,6 0,4 via Pulping & Fermentation via Gasification and Synthesis 0,2 0 0 20 40 60 80 100 120 140 Biomass price [ /Mg] dry basis Folie 17
Grade of Carbon Utilisation for Ethanol Production 100 % Ethanol is produced from lignocellulose biomass (LCB) synthesis with heterogenous Rhodium catalyst auxiliary power is not included 27 % 35 % 42 % C in biomass (LCB) EtOH from fermentation (state of the art) EtOH from fermentation (theoretically) EtOH from gasification and catalyt. synthesis Folie 18