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Prospects for the Development of Drop-in Liquid Biofuels (especially Gasoline)
from Sustainable Feedstocks
Reinhard Seiser
Andrew BurkeAndrew Burke
Session 1: Biofuel and Biomethane Transportation FuelsSession 1: Biofuel and Biomethane Transportation Fuels -Setting the Stage
Workshop: Assessment of Critical Barriers and Opportunities to AccelerateBiofuels and Biomethane as Transportation Fuels in California
University of California, San Diego Davis , September 17th, 2015
Biomass ResourceSource: http://www.nrel.gov/gis/mapsearch/
The difference between technical and gross resources arises from inaccessible or sensitive
Laird et al., Long-term impacts of residue harvesting on soil quality:
areas, losses from harvesting, and maintaining soil quality.
on soil quality:“Harvesting 90% of above ground residue [corn stover] for 19 years resulted in substantial degradation of soil quality. Organic C and total N were reduced.”
Willi R B B M J ki d S R K ffk (2015) A A t
University of California, San Diego Davis , September 17th, 2015
Williams, R. B., B. M. Jenkins and S. R. Kaffka (2015). An Assessment of Biomass Resources in California, 2013 Data - DRAFT. CEC PIER Contract 500-11-020, California Biomass Collaborative.
Transportation Fuels in California
Ethanol 2014 Biofuel production
Diesel
2020 Projections (ARB Target)
Potential from 30 MDT/yr (40% eff.)
2014 Total Consumption
Gasoline
0 5,000 10,000 15,000 20,000
Total
→ Strong need for renewable-gasoline production→ Additional biomass resources and efficiency gains needed
Million gal/yr
University of California, San Diego Davis , September 17th, 2015
→ Additional biomass resources and efficiency gains needed(energy crops, imports from other states, methanation of CO2)
Biomass CompositionConverted to moles: (CH1.43O0.65)n (daf) or ~ (CH2O)n (waf)40%
50%
60%
Redwood Mill Residue ( 2 )n ( )
daf…dry and ash freewaf…wet and ash free
20%
30%
40%Almond Prunings
Almond Shells
Walnut Shells
Corn Stover
0%
10%
Ash w% (dry)
Carbon w% (daf)
Hydrogen w% (daf)
Oxygen w% (daf)
Corn Stover
Cotton Stalks Ash: Si, K, Na, Ca, Mg, Al, Fe, and other metals.Inorganics: N, S.
% (d y) % (da ) % (da ) % (da )
Cellulose (C6H10O5)n, 40-50% Hemicellulose (~C5H8O4)n, 20-35% Lignin (~C31H34O11)n, 15-35%
University of California, San Diego Davis , September 17th, 2015
Biomass ~(CH2O)
Biomass ConversionVehicle FuelsBiomass, (CH2O)n Vehicle Fuels
Natural GasMethane, CH4CO2 CH4
(+C+H2O)
Methanol, AKI: 99, CH3OHC+CO2 CH3OH
Diesel components
Ethanol, AKI: 99, C2H5OH
C
CO2 C2H5OH
Gasoline components
C
Hexadecane, C16H34~CH2CO2+H2O
Isooctane, AKI: 100, C8H18
Toluene, AKI: 114, C7H8
~CH2CO2+H2O
Ethanol AKI: 99 C H OH
University of California, San Diego Davis , September 17th, 2015
(No n-Heptane, AKI: 0, C7H16 )
Ethanol, AKI: 99, C2H5OH
AKI…Anti-knock index, (RON+MON)/2
Many Players in the Area of Biomass Conversion
University of California, San Diego Davis , September 17th, 2015
Source: US DOE
Lignocellulosic Biomass
Conversion Technologiesg
HydrotreatingPyrolysis H2
DieselNaphtha
CRI (IH2)
Coolplanet
Refinery Gasoline
Kior
Diesel
Direct Liquefaction
Gasification
HydropyrolysisH2
Syngas (H2, CO, HC, tars, CO2) Gas Cleanup Methanation
CO2
RNG
CO2
CRI (IH )
TCG, REII, KITGobigas
Gasoline (blendstock)
Indirect Liquefaction
RNGG4 Insights
Gasification Gas Cleanup Methanation
Fisher Tropsch
RNG
Diesel
Fulcrum (TRI, tubular FT)
Jet Fuel
Middle distillate Hydroprocessing
Red Rock (Velocys)Frontline
Naphtha
Methanol/DME
Mixed-alcohol Synthesis
Methanol or DME
Ethanol
Haldor Topsoe (Tigas)
Refinery
Gasoline
Enerkem
TUV, West Biofuels
Methanol-to-Gasoline Gasoline (blend stock)
Haldor Topsoe (Tigas)
Fermentation of CO
Lanzatech Other Feedstocks or Methods
University of California, San Diego Davis , September 17th, 2015
HydrotreatingH2
Vegetable OilsNeste
Diesel
Price Components of Gasoline
• To be price competitive, cost of conversion needs to be near difference between imported crude oil plus refining and biomass costs.
• Other large benefits such as jobs, energy security, forest management, fire hazard g j gy y gmitigation, pollution, and greenhouse gas reduction would accrue.
Source: US DOE
University of California, San Diego Davis , September 17th, 2015
Financial Barrier: Scale-up RiskPre-commercial Demonstration
ScalePilot ScaleLaboratory
ScaleCommercial
Scale
$1M $10M $100M $1BCapital CostA l F l
oss
Plant SizeToo large scale up
Annual Fuel Production
1 gal 100s of gal 1 million gal >100 million gal
e P
rofit
s/Lo
Miscalculation of Valley-
Too large scale-up
Cum
ulat
ive sca cu a o o a ey
of-Death can turn a near-profitable projection into the worst-case scenario.Better to scale up in
smaller stepsC smaller steps
University of California, San Diego Davis , September 17th, 2015
Range Fuels: 5 tons/day → 125 tons/day (Phase1) … failedKior: 50 times from demonstration to commercial … on hold
Technical Barrier: Catalyst Deactivation
Contaminant Methanol Synthesis FT SynthesisMixed Alcohol Synthesis
Fixed‐/ Fluidized‐bed Methanation
Particulate < 0.02 mg/Nm3 n.d.(soot, dust char, ash)Tars (condensible) < 0.1 mg/Nm3 < 10ppbInhibitory compounds < 1 ppm < 1/1000ppmy p pp / pp
(class 2‐heteroatoms, BTX)Sulfur < 1 mg/Nm3 < 10ppb < 300ppm < 10/10ppb
(H2S, COS)Nitrogen < 0.1 mg/Nm3 < 20ppbNitrogen < 0.1 mg/Nm3 < 20ppb(NH3, HCN)
Alkali < 10 ppbHalides (primarily HCl) < 0.1 mg/Nm3 < 10 ppb
ppm parts per million ppb parts per billion
Many thermo-chemical processes employ catalysts and are subject to catalyst deactivation. High demands on gas cleanup.
ppm…parts per million, ppb…parts per billion
University of California, San Diego Davis , September 17th, 2015
Kior: Reports indicated 75% reduction of planned output.
Feedstock Barrier: Scale and Logistics
• Biomass is distributed and biomass facilities are small.• Refineries are concentrated and large. Fuel specifications for gasoline are tight.• Possibly combine process streams after they are being concentrated in energy:
Thermo-chemical conversion Refinery
Gasoline, Diesel, Pretreatment
Woody Biomass
Small scale Medium scale Large scale
Jet fuel
Pretreatment
Pretreatment
Thermo-chemical conversion
Thermo-chemical conversion
Pretreatment could be drying, torrefaction, or
Thermo-chemical conversion could be pyrolysis, or
Refining could be hydrocracking, hydrotreating,
University of California, San Diego Davis , September 17th, 2015
pyrolysis gasification+synthesis isomerization, distillation, sulfur removal
Conclusions
• Without drop-in biofuels from lignocellulosic biomass, itwill be difficult to meet renewable fuel targets for 2030will be difficult to meet renewable fuel targets for 2030.
• Facilities/processes to produce hydrocarbon drop-infuels are in an early stage of development.fuels are in an early stage of development.
• A number of pathways are being developed with plansfor demonstration projects.
• Financial, technical, and logistical barriers exist fornear-term commercialization of drop-in fuel production.
University of California, San Diego Davis , September 17th, 2015