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John HolladayPacific Northwest National Laboratory

PO Box 999, MSIN: P8-60, Richland, WA [email protected]

Hydrocarbon Drop-In BiofuelsEngine Research CenterUniversity of Wisconsin-MadisonJune 8, 2011

PNNL-SA-77610

• At low % of total market supply & demand, refiners can adapt

• As % blend increases, issues arise in refining and blending:

• Refinery “balance” (light / heavy, H2, octane, vapor pressure, …)

• Petrochemical feedstocks(naphtha, pen-hex, BTX, light paraffins & olefins, …)

• Ethanol competes with gasoline, batteries, H2, and mass-transit, while only liquid fuels compete in most diesel & jet markets

Energy Security and MarketSupply & Demand Balance

Source: Energy Information Administration, “Oil: Crude Oil and Petroleum Products Explained” and AEO2009, Updated February 2010, Reference Case.

Dr. Paul Bryan

DOE-EERE Advanced Biofuels ConsortiaNABC—Lignocellulosics, NAABB—Algae

Solix BiofuelsCoyote Gulch

Texas A&MPecos Site

National Alliance for Advanced Biofuels and Bioproducts

Slide 4

H3C CH3CH3CH3

UOP 5076-06

Natural Oils—Options like Ecofining: Product is a High Quality Pure Hydrocarbon

CH3HO

O H2

CO2

H2O +

+ H3C CH3

H3C CH3

HC

O

O

O

O

O

O

CH3

CH2+CH3

CH3H2O

CO2 H3C

H3C H3C CH3

CH3H3C

ReactorSystem

Water

CO2

Propane & Light Ends

Green Diesel

Product

Make-up Hydrogen

Separator

Feed

Acid Gas Removal

Green Naphtha

or Jet

2.2 – 3.5%

UOP Catalyst

Triglyceride

Free Fatty Acid

Straight Chain Paraffins

+H3C CH3

+

CH3CH3

CH3H3C

CH3 H3CCH3

Green Diesel

& Green Naphtha

Propane

National Advanced Biofuels Consortium

The National Advanced Biofuels Consortium (NABC) is a collaboration among U.S. Department of Energy national laboratories, universities, and private industry that is developing technologies to produce infrastructure-compatible, biomass-based hydrocarbon fuels.

NABC : For Open Distribution

http://www.eere.energy.gov/

http://www.recovery.gov/

http://www.anl.gov/index.html

http://www.lanl.gov/

Picture courtesy of http://www.bantrel.com/markets/downstream.aspx

Crude Oil Refinery: Infrastructure Conversion

NABC Strategies and Technologies

Converting biomass into infrastructure- compatible materials

Fermentation of Lignocellulosic Sugars

Team led by Amyris

RENEWABLE CHEMICALS AND FUELSANY FEEDSTOCK

INDUSTRIAL SYNTHETIC BIOLOGY PLATFORM

NABC: For Open Distribution

FLS Process Strategy Overview


Mevalonate Pathway

YEAST CELL

hydrolysate

Diesel & Chemical Precursor

FarneseneSynthase

Farnesene

[1] [2] [3] [4]

[1] Cane juice[2] Fermentation broth[3] Separations[4] Purification

Results: Dilute Acid/Enzyme Hydrolysis of Pine


Acid PretreatedLow severity: 190°C, 3 minutes, 0.63% sulfuric acid in liquid

Acid PretreatedHigh severity: 210°C, 3 minutes, 1.0% sulfuric acid in liquid

Catalysis of Lignocellulosic Sugars

Team led by Virent




Process options to produce hydrocarbons from lignocellulosic sugars



Sugar Hydrolysate

BioReformate

Heating biomass can give a bio-oil or synthesis gas

Fast Pyrolysis (reference)Ambient pressure T = 400-600 C Residence times 0.5 sOil yields around 70% (wt%)

Fast pyrolysis oil:High water content: 15-30%High O content: 35-40%High acidity; pH = 2.5, TAN > 100 mg KOH/g oilUnstable (phase separation, reactions)Low HHV: 16-19 MJ/kg


Bio-Oil

SynGas

Biomass

Heat

Vapor

Bio-Char

Fast pyrolysis oil is converted to fuels in a 2-step process (reference case)

The carbon recovery based on bio-oil was about 50%Holmgren, J. et al. NPRA national meeting, San Diego, March 2008.


HC

light products

mediumproducts

heavyproducts

H2

HT

H2O aqueousbyproduct

Hydroprocessed Bio-oil (from Mixed Wood)

PetroleumGasoline

Min Max Typical

Paraffin, wt% 5.2 9.5 44.2

Iso-Paraffin, wt% 16.7 24.9

Olefin, wt% 0.6 0.9 4.1

Naphthene, wt% 39.6 55.0 6.9

Aromatic, wt% 9.9 34.6 37.7

Oxygenate, wt% 0.8

Hydroprocessed Bio-oil makes jet fuel range fuels

0

10

20

30

40

50

60

70

80

90

0 50 100 150 200 250 300 350

perc

ent d

istil

led

temperature, degrees Celsius (corrected to 1 atm)

batch 1

batch 2

naphtha

jet

44.2% 42.4%


Catalytic Fast Pyrolysis

UOP leads the team


Replace sand (heat transfer medium) with catalysts



Standard Fast Pyrolysis



Hydropyrolysis

RTI—Team Lead


RTI’s Transport Reactor SystemAdd H2 (reactive gas) during pyrolysis

Hydropyrolysis

Reactive gas to cap intermediates in pyrolysis vaporCatalytically enhanced hydrogen transfer to reduce oxygen content Use of process modeling to explore commercial concepts


Hydropyrolysis -Preliminary Screening Results

Improved hydrocarbon yields through effective catalytic hydrogen-transfer


Gas / P (psi)

Catalyst Char Yield (wt%)

He / 400 none 10.5

H2 / 400 none 21.0

H2 /400 2wt% DCat-CS1 21.8

Hydrothermal Liquefaction

PNNL—Team Lead

HydrothermalLiquefaction

Liquid hydrocarbons

H2

Catalyticupgrading

solids

Wet biomass

~350ºC, 200 atm, biomass slurry in waterminutes


Slow pyrolysis in pH-moderated, pressurized water

Hydrothermal Liquefaction –


biomass slurry in water~350ºC, 200 atm, residence time of minutes

Hydrothermal Liquefaction – Preliminary Results


Wood Wet feed (9.4 wt%) feed operated for 8 h @ temp and pressure45 g/h separated oil; 30% mass oil yield, 53% on carbon basis

10.9% oxygen on dry basis, 30 TAN, 9.8% moisture0.2% nitrogen, 0.01% sulfur, 0.03% ash, 0.34% solids

12% carbon conversion to gasgas 82% CO2, 12% H2, 6% CH4 and higher hydrocarbon

35% carbon in aqueous, 4.6 pH effluent; 44,000 ppm COD

Corn Stover 11.1 wt% double wet grind feed operated for 8 h @ similar conditions51 g/h separated oil ~1 wt% nitrogen in oil

Feedstock Composition

Operating Conditions

Measured Conversion Yields

Process Model inAspen Plus

Flow rates

Process Economics usingDiscounted Cash Flow Analysis

with Capital and Operating Costs

Fuel Product Yield

Cost $gal

Minimum FuelSelling Price

Analysis Team


R&D TEA LCA


Critical Issues Addressed

Critical Success Factors

Example Biochemical Targets (end Stage II)

Example Thermochemical Targets (end Stage II)

Acceptable fuels &intermediates quality demonstrated

TAN<0.5, O content < 0.2Final products show potential to meet ASTM standards

Intermediates pass 60 day stability testPotential for commercialreadiness demonstrated

Process is ready to pilot based on MB closure, scale/reproducibilityof data and well-defined operations

Reduced carbon footprint compared to fossil based fuels

Process achieves >50% GHG reduction compared to gasoline, jet or diesel benchmark

Carbon & energyefficiency maximized

Carbon and energy efficiency demonstrated to be >50%

Capital and operatingcosts minimized

-Reduction in cellulase cost contribution>50%-Feed concentration to reactor>50%

Reactor RT <5 sec (CFP)Reactor P < 500psig (HYP)

Catalyst/organismrobustness

-95% conversion of carbohydrate portion -Inhibitory compounds identified/mitigated

Lifetime >1 yearLoading <5:1

Toxicity levels < EPA limits

Analytical methods developed to identify compounds27

General ConclusionShift of emphasis at DOE (EERE) toward the fuels that should be produced from biomass resources (emphasis on replacing the “whole barrel of oil”NABC and NAABB leading in technology development (NAABB has a feedstock focus on algal oils and biomass; NABC a conversion focus)NABC emphasis on integration with refinery—use of infrastructure in place to make and deliver those fuels into our vehicle fleet todaySix technologies are being examined, pilot ready technology will be delivered at the conclusion


Questions

Special Acknowledgement to National Advanced Biofuels Consortium (NABC)

Led by the National Renewable Energy Laboratory Tom Foust (PI)

National Alliance for Advanced Biofuels and BioproductsLed by Danforth Plant Sciences Center / Los Alamos National (NAABB)Jose Olivares (PI)

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http://nabcprojects.org/ http://www.naabb.org/

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