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National Renewable Energy Laboratory
Biomass GasificationBiomass GasificationOverviewOverview
Presented by Richard L. Bain
January 28, 2004
Operated for the U.S. Department of Energy by Midwest Research Institute • Battelle
Office of the Biomass ProgramOffice of the Biomass Program
GoalsGoalsReduce U.S. dependence upon foreign sources of petroleumRealization of the Industrial Biorefinery
MissionMissionTo foster research and development on advanced technologies to transform our abundant biomass resources into clean, affordable, and domestically-produced biofuels, biopower, and high-value bioproducts for improving the economic development and enhancing the energy supply options of the U.S.
The Unique Role of Biomass
While the growing need for sustainable electric power can be met by other
renewables…
Biomass is the only renewable that can meet our demand for carbon-based
liquid fuels and chemicals
Research Focus for the Biorefinery
Thermochemical Platform
Sugar Platform
BiomassCombined Heat & Power
Residues
Clean Gas
Conditioned Gas
Sugar Feedstocks
Advanced Biomass R&D
Systems Integration
Fuels, Chemicals, & Materials
Integrated Industrial Biorefineries
Thermochemical Platform Costs for SynGas Intermediate Impact of Overcoming Technical Barriers
0
2
4
6
8
10
12
14
16
18
20
Base550 tpd
Nth plant
Feed Handling
ThermochemicalConversion
Gas Conditioning
Sensors & Controls Process Integration
Cos
t of P
rodu
ctio
n ($
/GJ)
Without IntegratedDemonstrations
With IntegratedDemonstrations
Reference: Hamelink and Faaij (2001)
Pioneer Plant Costs
Performance SpecificPerformance SpecificProgram GoalsProgram Goals
Year 2003 2005 2010 2015 2020 2025 2030Minimum Syngas Selling Price ($/GJ, LHV) 9 8.3 6 5.6 5.1 4.7 4.3
Corresponding H2 cost ($/kg) 2.16 1.98 1.26 1.17 1.08 0.99 0.90jproduct, e.g., methanol ($/gal)
1.30 1.20 0.90 0.70 0.65 0.60 0.54
Feedstock cost ($/dry ton delivered) 30 30 30 30 30 30 30
Plant size (dry tons/day) 550 550 2,000 2,000 2,000 2,000 4,000
Feed Preparation/Gasification: 10% reduction in product cost by 2010
Gas Cleanup: 20% reduction in product cost by 2010
System Integration: 10% reduction in product cost by 2010
Strategic FitStrategic Fit
Gasification Cleanup Synthesis
Conversionor Collection Purification
Separation Purification
Pyrolysis
OtherConversion *
Biomass
Biomass Thermochemical ConversionFor Fuels and Chemicals
* Examples: Hydrothermal Processing, Liquefaction, Wet Gasification
PRODUCTS
• Hydrogen• Alcohols• FT Gasoline• FT Diesel• Olefins• Oxochemicals• Ammonia• SNG
• Hydrogen• Olefins• Oils• Specialty Chem
• Hydrogen• Methane• Oils• Other
Basic DefinitionsBasic Definitions
Biomass is plant matter such as trees, grasses, agricultural crops or other biological material. It can be used as a solid fuel, or converted into liquid or gaseous forms for the production of electric power, heat, chemicals, or fuels.
Black Liquor is the lignin-rich by-product of fiber extraction from wood in Kraft (or sulfate) pulping. The industry burns black liquor in Tomlinson boilers that 1) feed back-pressure steam turbines supplying process steam and electricity to mills, 2) recover pulping chemicals (sodium and sulfur compounds) for reuse.
Poplar Corn Stover Chicken Litter Black LiquorProximate (wt% as received)
Ash 1.16 4.75 18.65 52.01Volatile Matter 81.99 75.96 58.21 35.26Fixed Carbon 13.05 13.23 11.53 6.11Moisture 4.80 6.06 11.61 9.61
HHV, Dry (Btu/lb) 8382 7782 6310 4971
Ultimate, wt% as received
Carbon 47.05 43.98 32.00 32.12Hydrogen 5.71 5.39 5.48 2.85Nitrogen 0.22 0.62 6.64 0.24Sulfur 0.05 0.10 0.96 4.79Oxygen (by diff) 41.01 39.10 34.45 0.71Chlorine <0.01 0.25 1.14 0.07Ash 1.16 4.75 19.33 51.91
Elemental Ash Analysis, wt% of fuel as received
Si 0.05 1.20 0.82 <0.01 Fe --- --- 0.25 0.05 Al 0.02 0.05 0.14 <0.01 Na 0.02 0.01 0.77 8.65 K 0.04 1.08 2.72 0.82 Ca 0.39 0.29 2.79 0.05 Mg 0.08 0.18 0.87 <0.01 P 0.08 0.18 1.59 <0.01 As (ppm) 14
Representative Biomass & Black Liquor Compositions
Representative Biomass and Coal PropertiesRepresentative Biomass and Coal Properties
Biomass 1 Biomass 2 Coal 1 Coal 2 Tar Sands
Name Wood Red Corn Cob Grundy, IL. No 4 Rosebud, MT AthabascaClassification HvBb sub B Bitumen
Proximate Analysis, wt% Dry Moisture 25-60 16 8.16 19.84 Volatile Matter 77-87 ca. 80 40.6 39.02 Fixed Carbon 13-21 -- 45.47 49.08 Ash 0.1-2 4 13.93 9.16Ultimate Analysis, wt % Dry C 50-53 45 68.58 68.39 83.6 H 5.8-7.0 5.8 4.61 4.64 10.3 N 0-0.3 2.4 1.18 0.99 0.4 Cl .001-0.1 -- 0.12 0.02 -- O 38-44 42.5 6.79 16.01 0.2 S 0-0.1 0 4.76 0.79 5.5 Ash 0.1-2 4 13.93 9.16
H/C Atomic Ratio 1.4-1.6 1.5 0.8 0.81 1.47 HHV, Dry, Btu/lb 8,530- 9,050 7,340 12,400 11,684 17,900
Biomass 1 Biomass 2 Coal 1 Coal 2 Tar Sands
Name Wood Red Corn Cob Grundy, IL. No 4 Rosebud, MT AthabascaClassification HvBb sub B Bitumen
Proximate Analysis, wt% Dry Moisture 25-60 16 8.16 19.84 Volatile Matter 77-87 ca. 80 40.6 39.02 Fixed Carbon 13-21 -- 45.47 49.08 Ash 0.1-2 4 13.93 9.16Ultimate Analysis, wt % Dry C 50-53 45 68.58 68.39 83.6 H 5.8-7.0 5.8 4.61 4.64 10.3 N 0-0.3 2.4 1.18 0.99 0.4 Cl .001-0.1 -- 0.12 0.02 -- O 38-44 42.5 6.79 16.01 0.2 S 0-0.1 0 4.76 0.79 5.5 Ash 0.1-2 4 13.93 9.16
H/C Atomic Ratio 1.4-1.6 1.5 0.8 0.81 1.47 HHV, Dry, Btu/lb 8,530- 9,050 7,340 12,400 11,684 17,900
Biomass 1 Biomass 2 Coal 1 Coal 2 Tar Sands
Name Wood Red Corn Cob Grundy, IL. No 4 Rosebud, MT AthabascaClassification HvBb sub B Bitumen
Proximate Analysis, wt% Dry Moisture 25-60 16 8.16 19.84 Volatile Matter 77-87 ca. 80 40.6 39.02 Fixed Carbon 13-21 -- 45.47 49.08 Ash 0.1-2 4 13.93 9.16Ultimate Analysis, wt % Dry C 50-53 45 68.58 68.39 83.6 H 5.8-7.0 5.8 4.61 4.64 10.3 N 0-0.3 2.4 1.18 0.99 0.4 Cl .001-0.1 -- 0.12 0.02 -- O 38-44 42.5 6.79 16.01 0.2 S 0-0.1 0 4.76 0.79 5.5 Ash 0.1-2 4 13.93 9.16
H/C Atomic Ratio 1.4-1.6 1.5 0.8 0.81 1.47 HHV, Dry, Btu/lb 8,530- 9,050 7,340 12,400 11,684 17,900
Biomass 1 Biomass 2 Coal 1 Coal 2 Tar Sands
Name Wood Red Corn Cob Grundy, IL. No 4 Rosebud, MT AthabascaClassification HvBb sub B Bitumen
Proximate Analysis, wt% Dry Moisture 25-60 16 8.16 19.84 Volatile Matter 77-87 ca. 80 40.6 39.02 Fixed Carbon 13-21 -- 45.47 49.08 Ash 0.1-2 4 13.93 9.16Ultimate Analysis, wt % Dry C 50-53 45 68.58 68.39 83.6 H 5.8-7.0 5.8 4.61 4.64 10.3 N 0-0.3 2.4 1.18 0.99 0.4 Cl .001-0.1 -- 0.12 0.02 -- O 38-44 42.5 6.79 16.01 0.2 S 0-0.1 0 4.76 0.79 5.5 Ash 0.1-2 4 13.93 9.16
H/C Atomic Ratio 1.4-1.6 1.5 0.8 0.81 1.47 HHV, Dry, Btu/lb 8,530- 9,050 7,340 12,400 11,684 17,900
Biomass 1 Biomass 2 Coal 1 Coal 2 Tar Sands
Name Wood Red Corn Cob Grundy, IL. No 4 Rosebud, MT AthabascaClassification HvBb sub B Bitumen
Proximate Analysis, wt% Dry Moisture 25-60 16 8.16 19.84 Volatile Matter 77-87 ca. 80 40.6 39.02 Fixed Carbon 13-21 -- 45.47 49.08 Ash 0.1-2 4 13.93 9.16Ultimate Analysis, wt % Dry C 50-53 45 68.58 68.39 83.6 H 5.8-7.0 5.8 4.61 4.64 10.3 N 0-0.3 2.4 1.18 0.99 0.4 Cl .001-0.1 -- 0.12 0.02 -- O 38-44 42.5 6.79 16.01 0.2 S 0-0.1 0 4.76 0.79 5.5 Ash 0.1-2 4 13.93 9.16
H/C Atomic Ratio 1.4-1.6 1.5 0.8 0.81 1.47 HHV, Dry, Btu/lb 8,530- 9,050 7,340 12,400 11,684 17,900
Biomass 1 Biomass 2 Coal 1 Coal 2 Tar Sands
Name Wood Red Corn Cob Grundy, IL. No 4 Rosebud, MT AthabascaClassification HvBb sub B Bitumen
Proximate Analysis, wt% Dry Moisture 25-60 16 8.16 19.84 Volatile Matter 77-87 ca. 80 40.6 39.02 Fixed Carbon 13-21 -- 45.47 49.08 Ash 0.1-2 4 13.93 9.16Ultimate Analysis, wt % Dry C 50-53 45 68.58 68.39 83.6 H 5.8-7.0 5.8 4.61 4.64 10.3 N 0-0.3 2.4 1.18 0.99 0.4 Cl .001-0.1 -- 0.12 0.02 -- O 38-44 42.5 6.79 16.01 0.2 S 0-0.1 0 4.76 0.79 5.5 Ash 0.1-2 4 13.93 9.16
H/C Atomic Ratio 1.4-1.6 1.5 0.8 0.81 1.47 HHV, Dry, Btu/lb 8,530- 9,050 7,340 12,400 11,684 17,900
Biomass 1 Biomass 2 Coal 1 Coal 2 Tar Sands
Name Wood Red Corn Cob Grundy, IL. No 4 Rosebud, MT AthabascaClassification HvBb sub B Bitumen
Proximate Analysis, wt% Dry Moisture 25-60 16 8.16 19.84 Volatile Matter 77-87 ca. 80 40.6 39.02 Fixed Carbon 13-21 -- 45.47 49.08 Ash 0.1-2 4 13.93 9.16Ultimate Analysis, wt % Dry C 50-53 45 68.58 68.39 83.6 H 5.8-7.0 5.8 4.61 4.64 10.3 N 0-0.3 2.4 1.18 0.99 0.4 Cl .001-0.1 -- 0.12 0.02 -- O 38-44 42.5 6.79 16.01 0.2 S 0-0.1 0 4.76 0.79 5.5 Ash 0.1-2 4 13.93 9.16
H/C Atomic Ratio 1.4-1.6 1.5 0.8 0.81 1.47 HHV, Dry, Btu/lb 8,530- 9,050 7,340 12,400 11,684 17,900
Basic DefinitionsPyrolysisPyrolysis
Basic Definitions
• Thermal conversion (destruction) of organics in the absence of oxygen • In the biomass community, this commonly refers to lower temperature
thermal processes producing liquids as the primary product• Possibility of chemical and food byproducts
GasificationGasification• Thermal conversion of organic materials at elevated temperature and
reducing conditions to produce primarily permanent gases, with char, water, and condensibles as minor products
• Primary categories are partial oxidation and indirect heating
Thermochemical ConversionOf Biomass and Black Liquor
LowPressure
0.2 MPa
HighPressure
ENSYNDynamotiveBTGFortum
Bio-OilChanging World
TechnologiesChemrec (O2)Noell
GTI (O2)Carbona (O2)HTW O2)Foster Wheeler (O2)
FERCO (Indirect)MTCI (Indirect)Pearson (Indirect)TUV (Indirect)
For CHP:TPS (Air)Carbona (Air)Lurgi (Air)Foster Wheeler (Air)EPI (Air)Prime Energy (Air)
Chemrec (Air)
Feed: Biomass Feed: Black LiquorFeed: Biomass
MTCI-also BlackLiquor
Gas Product: PNNL Wet Gasification (CH4/H2)
10-25 MPa 1- 3 MPa 2 – 3 MPa
SyngasProductDry Ash Slag
Low(300-600°C)
Medium(700-850°C)
High(900-1200°C)
Temperature
Technical Barrier AreasTechnical Barrier AreasHydrogen
& BioproductsFuels
& ChemicalsExport
ElectricityBiomass ResiduesDedicated Crops
Feed Processing& Handling
Gasification&
Pyrolysis
GasConditioning& Separation
SyngasUtilization
Heat& Power
Generation
BiorefineryResidues
Feed Processing and HandlingGasification / ConversionGas Cleanup and Catalytic ConditioningSyngas UtilizationProcess IntegrationProcess Control, Sensors, and Optimization
Critical IssuesCritical Issues
Biomass Thermochemical ConversionPrimary Technical Barriers
Gasification Pyrolysis Black Liquor Gasification
• Feed Pretreatment- Feeder reliability- Feed modification
• Gasification- Tar & Heteroatom chemistry- Gasifier Design
• Gas Cleanup & Conditioning- Catalytic Conversion- Condensing Cleanup- Non-condensing Cleanup
• Syngas Utilization- Cleanliness requirements- Gas composition
• Process Integration• Sensors and Controls
• Oil Handling- Toxicity- Stability- Storage- Transportation
• Oil Properties- Ash- Acidity
• Oil Commercial Properties- Commercial Specifications- Use in Petroleum Refineries
• Containment- Metals- Refractories- Vessel design- Bed behavior/agglomeration
• Mill Integration - Steam- Power- Causticizing
• Fuels Chemistry- Carbon management- Tars- Sulfur management- Alkali management- Halogen management
• Sensors and Controls
Representative Gasification PathwaysRepresentative Gasification Pathways
Acid GasRemoval
Feed Preparation& Handling
Synthesis
ProductCO2
CatalyticConditioning& Reforming
CompressionLP IndirectGasification
Biomass ShiftConversion CompressionLow Pressure
Gasification
LP IndirectGasification
Compression& Reforming
Cold GasCleanup
Hot GasCleanup
High PressureGasification
Oxygen
CompressionReforming
Pyrolysis
Reduction
Combustion
Gas, Tar, Water
Ash
Biomass
Air
C + CO2 = 2COC + H2O = CO + H2
C + O2 = CO24H + O2 = 2H2O
Updraft Gasifier
Pyrolysis
Reduction
Combustion
Gas, Tar, Water
Ash
Biomass
Air
C + CO2 = 2COC + H2O = CO + H2
C + O2 = CO24H + O2 = 2H2O
Updraft Gasifier
Biomass
Pyrolysis
Reduction
Combustion
Gas, Tar, Water
AshAir
C + CO2 = 2COC + H2O = CO + H2
C + O2 = CO24H + O2 = 2H2O
Downdraft Gasifier
Biomass
Pyrolysis
Reduction
Combustion
Gas, Tar, Water
AshAir
C + CO2 = 2COC + H2O = CO + H2
C + O2 = CO24H + O2 = 2H2O
Downdraft Gasifier
Freeboard
Fluid Bed
PlenumAir/Steam
Biomass
Ash
Cyclone
Fluid-Bed Gasifier
Freeboard
Fluid Bed
PlenumAir/Steam
Biomass
Ash
Cyclone
Fluid-Bed Gasifier
Biomass
N2 or Steam
Furnace
Char
Recycle Gas
Flue Gas
Entrained Flow Gasifier
Air
Biomass
N2 or Steam
Furnace
Char
Recycle Gas
Flue Gas
Entrained Flow Gasifier
Air
Secondary
Circulating Fluid-Bed Gasifier
Fly Ash
Bottom Ash
Biomass
Air/Steam
GasifierPrimaryCyclone
CycloneSecondary
Circulating Fluid-Bed Gasifier
Fly Ash
Bottom Ash
Biomass
Air/Steam
GasifierPrimaryCyclone
Cyclone
Fly Ash
Bottom Ash
Biomass
Air/Steam
GasifierPrimaryCyclone
Cyclone
Community Power Corporation’sCommunity Power Corporation’sBioMax 15 Modular Biopower SystemBioMax 15 Modular Biopower System
FERCO GASIFIERFERCO GASIFIER-- BURLINGTON, VTBURLINGTON, VT
350 TPD350 TPD
Carbona Project: Skive, DenmarkCarbona Project: Skive, Denmark
BIOMASSBIOMASS
ASHASH
AIRAIR
ASHASH
POWERPOWER
HEATHEAT
FUELFUELFEEDINGFEEDING
GASIFIERGASIFIERTAR CRACKERTAR CRACKER
GAS COOLERGAS COOLER GAS COOLERGAS COOLERSTACKSTACK
HEAT RECOVERYHEAT RECOVERY
GAS TANKGAS TANK
GAS ENGINE(S)GAS ENGINE(S)
Typical Gas Heating ValuesTypical Gas Heating Values
Gasifier Inlet Gas Product Gas Product GasType HHV
MJ/Nm3
Partial Oxidation Air Producer Gas 7Partial Oxidation Oxygen Synthesis Gas 10Indirect Steam Synthesis Gas 15
Natural Gas 38Methane 41
Gas composition versus reactor typeGas composition versus reactor type
Gasifier FERCO Carbona Princeton IGTModel
Type Indirect CFB Air FB Indirect FB PFBAgent steam air s team O2/steamBed Material olivine sand none alum inaFeed w ood chips w ood pelle ts black liquor w ood chips
Gas Com position H2 26.2 21.70 29.4 19.1 CO 38.2 23.8 39.2 11.1 CO2 15.1 9.4 13.1 28.9 N2 2 41.6 0.2 27.8 CH4 14.9 0.08 13.0 11.2 C2+ 4 0.6 4.4 2.0GCV, MJ/Nm 3 16.3 5.4 17.2 9.2
Gas composition versus reactor typeGas composition versus reactor type
Gasifier Tech Univ Free Univ Univ of USEPA IGTVienna of Brusse ls Zaragosa
Type Indirect FB Air FB Dow ndraft Updraft PFBAgent steam air air air O2/s teamBed Material s ilica s ilica none none alum inaFeed w ood chips w ood chips w ood chips w ood chips w ood chips
Gas Com position H2 31.5 9 - 11 16 10 19.12 CO 22.7 15 - 17 21.5 14.8 11.07 CO2 27.4 18 14.4 12.8 28.88 N2 2.8 Diff 44.4 28.9 27.77 CH4 11.2 5 - 7 3.3 4.9 11.21 C2+ 4 3 NA NA 1.95
Gasifier TypesGasifier Types--Advantages and DisadvantagesAdvantages and Disadvantages
Gasifier Advantages Disadvantages Updraft Mature for heat
Small scale applications Can handle high moisture No carbon in ash
Feed size limits High tar yields Scale limitations Producer gas Slagging potential
Dow ndraft Small scale applications Low particulates Low tar
Feed size limits Scale limitations Producer gas Moisture sensitive
Fluid Bed Large scale applications Feed characteristics Direct/indirect heating Can produce syngas
Medium tar yield Higher particle loading
Circulating Fluid Bed Large scale applications Feed characteristics Can produce syngas
Medium tar yield Higher particle loading
Entrained Flow Can be scaled Potential for low tar Can produce syngas
Large amount of carrier gasHigher particle loading Potentially high S/C Particle size limits
Typical Gas, Contaminant YieldsTypical Gas, Contaminant Yields
Hybrid Poplar Switchgrass Mixed WoodsH2, vol % 33.99 24.31 31.82CO 36.67 39.47 31.59CO2 17.91 14.97 17.96CH4 12.56 13.77 11.73C2H4 4.41 5.86 4.50Benzene 1.35 0.96 1.06Toluene 0.31 0.20 0.24H2/CO 0.93 0.62 1.01H2S, ppmv 64-72 323-396 36-63Ammonia, ppmv 290 max 760 max 339-369Cl- cond, ppm-m/v 0 486 max 4 maxK+ cond, ppm-m/v 10 max 208 max 7 maxTot org. C cond ppm-m/v 2060 max 2320 max 2480 maxCyanide, ppm-m/v 37 1442-1472 ND
Tertiary ProcessesSecondary ProcessesPrimary Processes
VaporPhase
SolidPhase
Low P
Low P
HighP
LiquidPhase High
P
Biomass Charcoal Coke Soot
PrimaryLiquids
PrimaryVapors
Light HCs,Aromatics,
& Oxygenates
Condensed Oils(phenols, aromatics)
CO, H2,CO2, H2O
PNA’s, CO, H2, CO2,
H2O, CH4
Olefins, AromaticsCO, H2, CO2, H2O
CO, CO2,H2O
Pyrolysis Severity
C o n v e n tio n a lF la s hP y ro ly s is(4 5 0 - 5 0 0 oC )
H i-T e m p e ra tu reF la s hP y ro ly s is(6 0 0 - 6 5 0 oC )
C o n v e n tio n a lS te a mG a s ific a tio n(7 0 0 - 8 0 0 oC )
H i-T e m p e ra tu reS te a mG a s ific a tio n(9 0 0 - 1 0 0 0 oC )
A c id sA ld e h y d e sK e to n e sF u ra n sA lc o h o lsC o m p le x O x y g e n a te sP h e n o lsG u a ia c o lsS y r in g o lsC o m p le x P h e n o ls
B e n z e n e sP h e n o lsC a te c h o lsN a p h th a le n e sB ip h e n y lsP h e n a n th re n e sB e n z o fu ra n sB e n z a ld e h y d e s
N a p h th a le n e sA c e n a p h th y le n e sF lu o re n e sP h e n a n th re n e sB e n z a ld e h y d e sP h e n o lsN a p h th o fu ra n sB e n z a n th ra c e n e s
N a p h th a le n e *A c e n a p h th y le n eP h e n a n th re n eF lu o ra n th e n eP y re n eA c e p h e n a n th ry le n eB e n z a n th ra c e n e sB e n z o p y re n e s2 2 6 M W P A H s2 7 6 M W P A H s
* A t th e h ig h e s ts e v e r ity , n a p h th a le n e ss u c h a s m e th y ln a p h th a le n e a res tr ip p e d to s im p len a p h th a le n e .
MixedOxygenates
PhenolicEthers
Alkyl Phenolics
HeterocyclicEthers PAH
LargerPAH
400 oC 500 oC 600 oC 700 oC 800 oC 900 oC
Chemical Components in biomass tars (Elliott, 1988)
Gasification ApplicationsGasification Applications
• Heat• District heating• Plant steam• Institutional heating
• Combined heat and power• Pulp and paper industry• District heating/electricity
• Electricity only• Cofiring - ash segregation• Integrated gasification combined cycle
• Synthesis gas• Oxygenates - methanol, ethanol, DME, etc.• Fischer-Tropsch Liquids• Hydrogen• Methane• Chemicals
Biorefinery Utilities ApplicationsBiorefinery Utilities Applications
Synthesis Gas Synthesis Gas -- Examples Examples of Conversion Processesof Conversion Processes
• Oxygenates• Methanol, DME, Mobil MTG• Mixed alcohols
• Snamprogetti/Topsoe, Lurgi, Dow, IFP/Idemitsu• Modified Fischer Tropsch - ethanol
• Dow, Pearson Technologies• Biochemical (fermentation)
• Mississippi State University, University of Arkansas• Hydrocarbon fuels
• Methane• Fischer Tropsch
• Iron based - Sasol Synthoil• Cobalt based - Shell middle distillate synthesis (SMDS)
• Hydrogen• Methane steam reforming• High and low temperature shift• H2 separation
SyngasCO + H2
Methanol
H2OWGSPurify
H2N2 over Fe/FeO
(K2O, Al2O3, CaO)NH3
Cu/ZnOIsosynthesis
ThO2 or ZrO2
i-C4
Alkali-doped
ZnO/Cr2 O
3
Cu/ZnO; Cu/ZnO/Al2 O3
CuO/CoO/Al2 O3
MoS2
MixedAlcohols
Oxosynthesis
HCo(CO)4
HCo(CO)3 P(Bu
3 )
Rh(CO)(PPh3 )3
AldehydesAlcohols
Fischer-Tropsch
Fe, C
o, R
u
WaxesDiesel
OlefinsGasoline
Ethanol
Co, Rh
FormaldehydeAg
DME
Al 2O
3
zeolites
MTOMTG
OlefinsGasoline
MTBEAcetic Acid
carb
onyla
tion
CH3O
H +
COCo
, Rh,
Ni
M100M85DMFC
Direct Use
hom
olog
atio
nCo
isob
utyl
ene
acid
ic io
n ex
chan
ge
BIOMASS SYNGAS
ETHANOL
FEEDPREP GASIFICATION CLEANUP &
CONDITIONING
BIOCONVERSION
SEPARATION
Ethanol From BiomassEthanol From Biomass
Thermochemical Syngas Thermochemical Syngas –– Biochemical EthanolBiochemical Ethanol
Fischer Fischer TropschTropsch SynthesisSynthesis
Coal,Natural Gas,or Biomass
Gasifier
Air, Oxygen,Steam
Gas Cleanupand Conditioning
Clean syngasH 2 and CO
High T FTS
Low T FTSSlurry (Co) orTubular (Fe)
Reactor
CFB or FFB (Fe)Reactor
Waxes (> C20)Hydrocracking
Diesel
Olefins(C3 - C11)
OligomerizationIsomerizationHydrogenation
Gasoline
Particulate RemovalWet ScrubbingCatalytic Tar ConversionSulfur ScrubbingWGSetc.
)1) CO + 3H2 CH4 + H2O (Methanation)
)2) nCO + (2n+1)H2 CnH2n+2 + nH2O (Paraffins)
)3) nCO + 2nH2 CnH2n + nH2O (Olefins)
)4) nCO + 2nH2 CnH2n+1OH + (n-1)H2O (Alcohols)
Simplified Methanol Synthesis Process Flow DiagramSimplified Methanol Synthesis Process Flow Diagram
DesulphurizationNaturalGas Steam Reforming
Steam, O2
syngas (CO/CO2/H2)
Compressor MethanolConverter
Coolingand
DistillationMethanol
syngas recycle loopPurgeGas
BioSyngas
CO + 2H2 CH3OH ∆Hr = -90.64 kJ/molCO2 + 3H2 CH3OH + H2O ∆Hr = -49.67 kJ/molCO + H2O CO2 + H2 ∆Hr = -41.47 kJ/mol
Preferred Stoichiometry: (H2 – CO2)/(CO + CO2) = 2
Heat and Power Heat and Power -- Prime MoversPrime Movers
Steam turbinesExtracting - for CHPNon extracting - electricity onlySmall to large scale
IC engines5 kW to 2 MWControl of NOx and CO
TurbinesMicroturbinesGas Turbines - GT and IGCC applications
Stirling engines
Fuel cells
Why Biomass + Fuel Cells?Why Biomass + Fuel Cells?Good temperature and pressure match
Attractive fuel gas characteristics
Allows penetration of fuel cells into markets withoutnatural gas distribution networks
High efficiency maximizes biomass conversion to electricity- reduces biomass demand for energy production
Fossil carbon substitution
Fuel Cells are "Reverse" Electrolysis
Fuel In Oxidant In
Depleted fuel Out Depleted Oxidant Out
PEMS
PAFC
MCFC
SOFC H
H O
2
2
O
H O
2
2
O
H O
2
2
O
CO
2
2
O2
H2
HCOH O
2
2
2
H2
CO3=
H+
H+
O=
Anode Cathode
Electrolyte(Ion conductor)
80ºC
200ºC
650ºC
1000ºC
Fuel Cell Schematic
Freeboard
Fluid Bed
PlenumAir/Steam
Biomass
Ash
Product Gas
Cyclone
Fluid-Bed Gasifier
GasCleanup
Compressor
CoolingAir
IsothermalPre-reformer
HRSG
A C
DC/ACInverter
ProcessWater
Exhaust
CarbonateFuel Cells
A.C.Output
Air
Burner
Research and Development AreasResearch and Development Areas(not all(not all--inclusive)inclusive)
• Feed characterization• Materials handling
• Storage• Conveying• Moisture control• Comminution• Feeding
• Gasification• Kinetics• Phase equilibria• CFD modeling
• Gas cleanup• Tar, ammonia, water• Particulates, ash• Residual carbon control• Integrated process specific species• Gas separations
• Process integration• Prime mover systems• Catalytic syngas conversion
• Sensors and controls• LCA and TE modeling
NREL FacilitiesNREL Facilities
MBMSMBMS
TMBMSTMBMS
Gasification (TCUF)Gasification (TCUF)
Engine TestingEngine Testing
EmissionsEmissionsMonitoringMonitoring
Thermochemical Process Development Unit (TCPDU)Thermochemical Process Development Unit (TCPDU)
Biomass Feed
8-in. FluidizedBed Reactor
Hopper/Feeder
Controller
SuperheatedSteam
ThermalCracker
Cyclones
Char
Settling Tank
Aqueous Effluent
Scrubber
BlowerCoalescing
Filter
Wet scrubbed Syngas
Base Configuration
TCPDU Process Conditions and TCPDU Process Conditions and Product Gas CompositionProduct Gas Composition
TCPDU process parameters 11-Feb-03 to 28-Feb-03steam feed rate (kg/h) 20.0 ± 0.2biomass feed rate (kg/h) 10.5 ± 0.9fluid bed T (ºC) 615 ± 1thermal cracker T (ºC) 775 ± 2product gas flow rate (kg/h) 8.2 ± 0.8material balance 98.9±10%
Average gas composition from indirect wood gasification in TCPDU
2/11 to 2/28/03
GC analysis of Port 3 (vol. %, N2- and steam-free)
hydrogen 26.9 ± 1.4 methane 15.6 ± 0.2 carbon monoxide 26.7 ± 1.4 carbon dioxide 23.5 ± 0.8 ethylene 4.1 ± 0.1 ethane 0.68 ± 0.07 acetylene 0.47 ± 0.04 propylene 0.32 ± 0.04 1-butene 0.16 ± 0.04 H2/CO ratio 1.0 ± 0.1 Tar concentrations by TMBMS (ppmv,
w/ steam and N2) benzene 1732 ± 165 toluene 715 ± 89 cresol 216 ± 44 naphthalene 327 ± 33 phenanthrene 72 ± 7
Averaged mass spectrum (TMBMS) of tars from indirect wood gasification
75 100 125 150 175 2000
2e+4
4e+4
6e+4
8e+4
1e+5 78
91,92
104 116
128
142 152 166 178
192 216
94
108 202
78 - benzene91,92 - toluene94 - phenol104 - styrene108 - cresol116 - indene128 - naphthalene
142 - methylnaphthalenes152 - acenaphthalene166 - flourene178 - anthracene/phenanthrene192 - methylanthracene?202 - pyrene/flouranthene216 - benzo(a)flourene
Experimental ApproachExperimental Approach
m /z
5 0 7 5 1 0 0 1 2 5 1 5 0 1 7 5 2 0 0 2 2 5
Inte
nsity
(arb
.)
- 2 0 0 0 0
- 1 5 0 0 0
- 1 0 0 0 0
- 5 0 0 0
0
5 0 0 0
1 0 0 0 0
1 5 0 0 0
2 0 0 0 0
2 5 0 0 0
C O 2 ( /1 0 )
b e n z e n e
t o lu e n e n a p h t h a le n e
p y r e n e
Difference Mass Spectrum (catalyst outlet-inlet) showing destruction of
biomass gasifier tars
Gas Flow Rate
0.35-0.4 kg/hr 7-18 kg/hr
WHSV (weight of feed/hr / weight of catalyst)
1.6 hr-1 0.16-0.48 hr-1
Temperature
700-900°C 850°C
5 cm bench-scale reformer – March, 2001 30 cm pilot-scale reformer – April 2002
Project StatusProject Status
RFPissued
1/03
Responsereceived
4/03
Revise scopeto reduce cost;Contract placed
6/03
Expecteddelivery
11/03
Installationcomplete
12/03
Catalyst testing
2/04-9/04
Scrubber
Cyclones
Tar Reformer
time-on-stream (h)
0 1 2 3 4 5 6 7
% c
onve
rsio
n
0
20
40
60
80
100
benzene
methane
850oC 825oC 800oC 775oC 750oC
Methane and benzene breakthrough vs. time-on-stream for temperature ramp experiments with NREL-1 catalyst.
time-on-srteam (h)
0 1 2 3 4 5 6 7
% c
onve
rsio
n
75
80
85
90
95
100
105
benz
ene
slip
(ppm
v)
0
500
1000
1500
2000
total tar
benzene slip(rt. axis)
850oC 825oC 800oC 775oC 750oC
Total tar conversion and benzene slip for NREL-1Catalyst during temperature ramp experiments
2FBR temperature (oC)
750 775 800 825 850
% c
onve
rsio
n
0
20
40
60
80
100
methane benzenetoluenenaphthalenephenan./anthr.cresol
NREL-1 Temperature Ramp
Steady State conversion of several tar species and methane for NREL-1 catalyst