Prospects for the Development of Drop-in Liquid Biofuels

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


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


→ 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%


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


(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


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


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


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


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


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,


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.


Documents

Prospects for the Development of Drop-in Liquid Biofuels