Valorisation of Synthesis Gas from Biomass - the Piteå DME pilot Esben Lauge Sørensen, May 2009
Contents Presentation of Haldor Topsøe A/S Presentation of Chemrec AB The BioDME Project Lay-out of DME pilot Gasifier Performance Syngas Technologies today and tomorrow Conclusion: Anticipated Technological Conquests
Presentation of Haldor Topsøe A/S
Topsoe SynGas Technologies Ammonia Hydrogen Methanol Formaldehyde DME Gasoline - TIGAS Synthesis Gas SNG 15-20% of turn-over spent on R&D
Topsoe Pilot Plant Traditions
Presentation of Chemrec AB - Technology -
Generation of Motor Fuels at a Pulp Mill Valorisation of black liquor: Production of syngas for motor fuel production from internal stream in existing pulp-mill Steam generation from biomass is used to make up energy content of produced biofuel Biomass Biomass boiler Steam and power Black liquor Pulp wood Pulp mill Green liquor Steam Cellulose pulp Power Motor fuels plant Motor fuel
Why Black Liquor Gasification? Liquid Easy to feed to a pressurized gasifier Can be atomized to fine droplets Rapid gasification rates Highly reactive (high Na/K content) Full carbon conversion at ~1000 deg C No tar formation Low methane formation BL is available in large quantities About 270 MW of black liquor is generated at an average sized pulp mill (~ 400 000 tons of pulp per year)
The BioDME Project An EU-sponsored bio-mass to liquid fuels project
The BioDME project 3G vehicle development Fuel injection development Vehicle production Vehicle field test Vehicle production Biomass Black liquor Syngas generation and cleaning Fuel properties DME production DME Distribution& filling Industrial use
BioDME project Consortium Partners - Plant engineering, construction and operation - Plant owner - DME injection system development - Laboratory support to plant operation - DME production technology provider - DME distribution - DME fuel specification - Fuel additives and lubricant developments BioDME Project Coordinator - Engine development - Vehicle manufacturing - Field test responsible
Pilot site: Piteå in Sweden Existing DP-1 DME Storage Planned DME Pilot
Pilot plant on location Architectural view of new plant
Process Technology Demonstration Timeline First EU-application filed: June 2007 Official Project Kick-off Sept 2008 Basic Engineering Complete: Mar 2009 Start of DME-production: June 2010 Test programme completed: Sept 2012
Pilot Plant: 5 MTPD DME from BLG
Overall Process Layout Existing unit
Performance of existing gasifier
Existing Gasification Pilot Plant, DP-1 Black Liquor Oxygen GAS COOLER STEAM GENERATOR Cooling water BFW * Cooled raw syngas REACTOR * QUENCH Raw syngas * LPsteam MPsteam Weak Wash Condensate * Cooling Water in DP-1
Raw gas Data from Development Plant H 2 CO CO 2 50-70 ppm benzene < 5ppm naphthalene Zero or close to zero tar contents Very little fouling in heat exchangers Particulates non-detectable CH 4
Black Liquor Gasification Typical performance Example: Data for liquor at 73% DS content as fired. LHV: MW th(lhv) Black liquor feed 75 MP and LP Steam generated 23 Feedwater heating 2 Syngas 44 Gasifier thermal efficiency 92% Replaces low-efficiency Tomlinson boiler with high-efficiency biomass boiler Temperature of gas [ C] 200 150 100 50 0 0 5 10 15 20 25 30 Effect from gas cooling/condensation [MW]
Topsoe Syngas Technologies - Now and in the future
Tailor-made catalysts and technologies Biomass gasification processes from 1 bar Slurry feed gasification At up to ~ 80 bar Process Variation
WGS a versatile reaction Steam/CO >2.5 IGCC H 2 S > 1% H 2 / CO >> H 2 T 0 ~240 C P ~80 bar Water Gas Shift (H 2 -CO)/(CO+CO 2 ) = 3 H 2 /CO = 1-2 NH 3 SNG (TREMP) MeOH/FT T 0 ~170 C P ~1 bar H 2 S < 0.01% CO/H 2 = 1 DME Gasoline (TIGAS) Steam/CO <1 23 Variety of Input Variety of Products
Water-gas shift catalysts from Topsøe Sweet shift catalysts High temperature shift: Fe/Cu/Cr Low to Medium temperature shift: Cu/Zn/Al SK-201-2 LK-811 LK-821 Sour shift catalysts High and low temperature service: supported Co Mo sulphides SSK-10
Energy efficient H 2 Production - industrial lay-out Heat integration
Acid Gas Recovery Units in Topsoe Plants Many technologies commercially available Simple activated MDEA wash used for pilot plant. A sulphur slip in the order of 20 wt ppm is anticipated. Absorption beds used together with amine wash to reach syngas quality demand In industrial scale, an AGR with a sulphur slip lower than 1 ppm will be used
Deep Desulpurisation of Synthesis Gas Sulphur components in synthesis gas (CO, CO 2, H 2 ) H 2 S (ppm), COS (ppm), Organic S (ppb) Removal of sulphur HTZ Contains ZnO Removal of H 2 S + COS at some conditions Syngas: H 2 + CO + CO 2 + Sulphur ST-101 Contains Cu, Zn and Al oxides Removal of all sulphur compounds Cu also promotes the formation of MeOH Operation at low temperature to avoid MeOH formation Catalyst S-guard Clean Syngas
Optimal Desulphurisation Temperature Dependence on temperature Methanol formation Volume needed Temperature
Methanol synthesis loop - industrial lay-out Off-gas to fuel H 2 recovery unit LP steam DMW Purge gas scrubber Make-up gas Sulphur guard Methanol reactor Recycle Off-gas to fuel HP separator LP separator Raw MeOH product
Methanol Synthesis under condensing conditions Equilibrium curve Two-phase region Dewpoint curve No condensation
Comparison of key process data - industrial vs. novel MeOH technology Industrial lay-out New technology Methanol capacity, index 100 100 M.U.-gas flow, (H 2 + CO), index 100 99 Reactor inlet flow, index 255 99 H 2 /CO inlet reactor ~ 5.5 2.3 CO/CO 2 inlet reactor ~ 3.8 6 Recycle ratio 1.6 0 (!) Catalyst volume, index 100 40-80
DME synthesis - industrial lay-out Off-gas Recycle DME column DME product Waste water column Methanol Reactor Waste water MP steam Steam condensate
Conclusion: Anticipated Technological Conquests
Conclusion Demonstration of a process for production of DME as diesel substitute from biomass via black liquor from a pulp mill Validation of concept through demonstration of entire value chain from black liquor gasification to the use as diesel substitute New standards for deep desulphurisation of synthesis gas, sour shift conversion and once-through methanol production