Overview of Liquid Biofuel Technologies

Dr. Michael A. Pacheco Director of the National Bioenergy Center National Renewable Energy Laboratory Golden, Colorado

prepared for TAPPI International Renewable Energy Conference, 10-11 May 2007

- ABSTRACT A wide array of biomass feedstocks and conversion technologies currently exist or are being developed for the production of liquid fuels from biomass. Each combination of a feedstock and conversion technology presents a different route for producing liquid fuel from biomass, and each of these routes is at a different stage of development. This presentation will provide an overview of the following conversion pathways: ligno-cellulose to ethanol, renewable diesel, bio-oil from pyrolysis, biomass-derived syngas to fuels, and triglyceride-derived fuels from aquatic species. What emerges is a continuum of options from the more mature near-term options, to lessmature longer-term technology options. The current status, strengths, weaknesses, opportunities and challenges of each route will be discussed. The presentation will include information from the latest economic assessments of these strategic biomass-based opportunities, where data are available. Finally, some ideas for integrating of these biomass conversion technologies into existing infrastructure within the petroleum, agriculture and/or forestry industries will also be discussed.

An Overview of Liquid Biofuels Technology

TAPPI 2007 International Conference on Renewable Energy Dr. Michael A. Pacheco Director of The National Bioenergy Center

The National Bioenergy Center

Supports the mission and goals of DOEs Biomass Program Develops technology to produce fuels, chemicals, materials, and power from biomass. Partners extensively with the emerging industry Works as a multi-laboratory consortium of:
Argonne National Laboratory (ANL) Idaho National Laboratory (INL) National Renewable Energy Laboratory (NREL) Oak Ridge National Laboratory (ORNL) Pacific Northwest National Laboratory (PNNL)

Headquartered at NREL with about 100 researchers and an annual core R&D budget of about $30 million

U.S. Biomass Resource Assessment

Updated resource assessment - April 2005 Jointly developed by U.S. DOE and USDA Referred to as the Billion Ton Study

Taken from ORNL & USDA Resource Assessment Study by Perlach et.al. (April 2005) http://www.eere.energy.gov/biomass/pdfs/final_billionton_vision_report2.pdf

Significance of the Billion Ton Scenario

Billion Barrel of Oil Equivalents

Based on ORNL & USDA Resource Assessment Study by Perlach et.al. (April 2005) http://www.eere.energy.gov/biomass/pdfs/final_billionton_vision_report2.pdf

Range of Possible Biorefinery Concepts

Biomass Feedstock Conversion Processes Products
Fuels Ethanol Biodiesel Green Gasoline & Diesel Power Electricity Heat Chemicals Plastics Solvents Chemical Intermediates Phenolics Adhesives Furfural Fatty Acids Acetic Acid Carbon Black Paints Dyes, Pigments, and Ink Detergents Etc. Food and Feed

Trees Grasses Agricultural Crops Residues Animal Wastes Municipal Solid Waste Algae Food Oils

Enzymatic Fermentation Gas/liquid Fermentation Acid Hydrolysis/ Fermentation Gasification Combustion Co-firing Trans-esterification

Near-term Focus on Ethanol

Near Term

Ethanol as a blending agent from either grain or cellulosic material from Ag and/or Forestry industry Biodiesel Transesterified vegetable oils blended with diesel Green Diesel/Gasoline fats, waste oils, or virgin oils blended with crude oil as a feedstock for making low-sulfur diesel/gasoline in petroleum refinery Pyrolysis Liquids as a boiler fuel or an alternative feedstock to petroleum refinery or gasification facility, also a future source of aromatics and/or phenols Synthesis Gas for conversion to Fischer Tropsch liquids, MeOH/DME, or mixed alcohols Algae as alternative source of triglycerides for biodiesel or green diesel

Long Term

Hydrocarbons from hydrogenation of carbohydrates or lignin

Integrated Cellulosic Ethanol Biorefinery

Focus of National Bioenergy Center

Reducing the Cost of Cellulosic Ethanol

$6.00

State of Technology Estimates

Minimum Ethanol Selling Price ($/gal)

$5.00

Enzyme Conversion Feedstock Current DOE Cost Targets President's Initiative Costs in 2002 Dollars

Feed $53/ton
$4.00

$3.00

$2.00

2005 Yield 65 gal/ton

$1.00

Feed $30/ton Feed $30/ton Yield 90 gal/ton Yield 94 gal/ton

10,000 TPD

$0.00 2000 2005 2010 2015 2020

Energy Required to Produce Ethanol

Total Btu spent for 1 Btu available at fuel pump
3
From Biomass

Btus Required per Btu of Fuel

From Coal and Natural Gas

Fuel-to-Petroleum Ratio = 10 45% Efficiency

2.5

From Petroleum

57% Efficiency Fuel-to-Petroleum Ratio = 0.9

1.5

81% Efficiency Energy in the Fuel

0.5

0 Gasoline Corn Ethanol Cellulosic Ethanol

Based on Well to Wheels Analysis of Advanced Fuel/Vehicle Systems by Wang, et.al (2005).

Other Near-Term Biofuel Technologies

Near Term

Ethanol as a blending agent from either grain or cellulosic material from Ag and/or Forestry industry Biodiesel Transesterified vegetable oils blended with diesel Green Diesel/Gasoline fats, waste oils, or virgin oils blended with crude oil as a feedstock for making low-sulfur diesel/gasoline in petroleum refinery

Long Term

Oils, Fats & Greases as Bio-renewable Petroleum Refinery Feedstocks

ISBL Petroleum Refinery Catalytic Cracker Oils and Greases Distillate Hydrotreater Green Diesel Green Gasoline & Olefins Co-processing of oils and greases with petroleum fractions Utilize existing process capacity Potential for lower conversion costs (than FAME) Higher quality diesel blending component G/D flexibility
Based on Presentations at 1st International Biorefinery Workshop, Washington DC, July 20-21, 2005 - Future Energy for Mobility, James Simnick, BP - From Bioblending to Biorefining, Veronique Hervouet, Total - Opportunities for Biorenewables in Petroleum Refineries, Jennifer Holmgren, UOP

Green Diesel

Hydrotreating of biorenewable oils in existing refinery units Lower capital costs than biodiesel Excellent fuel properties
Source: U.O.P. Corp. 1st International Biorefinery Conference, August 2005

Published Economic Comparison

(from UOP-NREL-PNNL study)
Net Present Value Biodiesel is least competitive option in this UOP/PNNL/NREL study All fuels from soy bean oil require fuel subsidy Green fuels or olefins from greases in petroleum refinery may generate positive NPV even without subsidy

Source: Arena, B. et.al., Opportunities for Biorenewables in Petroleum Refineries, presented at Rio Oil & Gas Conference, held Sept 11-14, 2006

Mid-Term Biofuel Technologies

Near Term

Ethanol as a blending agent from either grain or cellulosic material from Ag and/or Forestry industry Biodiesel Transesterified vegetable oils blended with diesel Green Diesel/Gasoline fats, waste oils, or virgin oils blended with crude oil as a feedstock for making low-sulfur diesel/gasoline in petroleum refinery Pyrolysis Liquids as a boiler fuel or an alternative feedstock to petroleum refinery or gasification facility, also a future source of aromatics and/or phenols Synthesis Gas for conversion to Fischer Tropsch liquids, MeOH/DME, or mixed alcohols

Long Term

Fast Pyrolysis and Bio-oil as Feed to Power Plant or Petroleum Refinery

Bio-oil is is comprised of many oxygenated organic chemicals, with water miscible and oil miscible fractions
Dark brown mobile liquid, Combustible, Not 100% miscible with hydrocarbons, Modest heating value ~ 17 MJ/kg, High density ~ 1.2 kg/l, Acidic, pH ~ 2.5, Pungent odour, Ages - viscosity increases with time
Based on research at NREL (1990 - 2006)

Crude Pyrolysis Oil Cost Estimates

80 12 $/Giga JouleJ 10 8 6 4 2 0
Base Case Incr size to Incr yield to 2000 tpd 70%
Source: V. Putsche, NREL report (2004)

Base Case:
550 ton/d wood chips 59% oil yield 2 MBPD oil product $ 44 million Capital

70 60 40 30 20 10 0 $/BOE 50

Decentralized Biomass Liquids Scenario

Alternate Feedstocks Petroleum Refinery

Mid-Term Biofuel Technologies

Near Term

Ethanol as a blending agent from either grain or cellulosic material from Ag and/or Forestry industry Biodiesel Transesterified vegetable oils blended with diesel Green Diesel/Gasoline fats, waste oils, or virgin oils blended with crude oil as a feedstock for making low-sulfur diesel/gasoline in petroleum refinery Pyrolysis Liquids as a boiler fuel or an alternative feedstock to petroleum refinery or gasification facility, also a future source of aromatics and/or phenols Synthesis Gas for conversion to Fischer Tropsch liquids, MeOH/DME, or mixed alcohols

Long Term

Gasification Offers Many Feed & Product Options

Primary Energy Source Syngas Step Conversion Technology Syngas to Liquids (GTL) Process Products
Diesel Naphtha Lubes

Natural Gas

Fischer Tropsch (FT)

Upgrading

Coal Syngas (CO + H2) Biomass

Syngas to Chemicals Technologies

Acetic Acid Methanol Hydrogen

Extra Heavy Oil

M ixed Alcohols (e.g. ethanol, propanol) Others (e.g. Triptane, DME, etc)

Slide courtesy of BP Corporation

Thermochemical Route to Alcohols

Biomass

Feed Handling and Conditioning

Dried Biomass

Gasification

Crude Syngas

Tar Reforming And Scrubbing

Scrubbed Syngas

Syngas Compression
High P Syngas

Mixed Alcohol Synthesis

Crude Products

Overall gas conditioning reactions Reforming: CxHyOz + H2O(g) C + H2O(g) H2 + xCO CO2 + H2 COx + H2

Methanol

Water gas shift: H2O + CO Gasification:

Preliminary Separation
Mixed Alcohols

2012 Targets for Tar Reforming: - Promoted metal/support catalyst - CH4 < 3 vol% - Benzene < 10 ppmv - Heavy tars < 1 g/nM3

Product Separation
C3 + Alcohols

Ethanol

Example 2030 Target Case for a Large Cellulosic Biorefinery to Maximize Ethanol
Corn Stover 10,000 dMT/day

Ethanol via Bioconversion

Steam & Power

Ethanol 1,035,000 gpd Lignin CHP Plant Ethanol 1,168,000 gpd 409 MM gal/yr Yield: 117 gal/ton

Lignin-Rich Residue 1,500 dMT/day Gasification

Lignin-Rich Residue 1,432 dMT/day Alcohol Synthesis

Syngas

Ethanol 133,500 gpd

Higher Alcohols S. Phillips and J. Jechura

19,100 gpd n-Propanol 7,300 gpd n-Butanol 3,300 gpd n-Pentanol

Thermochemical Ethanol Cost Targets

$2.50

State of Technology Estimates

Conversion Feedstock Previous DOE Cost Targets President's Initiative Costs in 2002 Dollars

Minimum Ethanol Selling Price ($ per gallon)

$2.00

Forest Resources 56 gal/ton

$1.50

Forest & Agricultural Resources 67 gal/ton

$1.00

$0.50

$0.00 2002 2005 2008 2011

D. Dayton

Longer Term Biofuel Technologies

Near Term

Ethanol as a blending agent from either grain or cellulosic material from Ag and/or Forestry industry Biodiesel Transesterified vegetable oils blended with diesel Green Diesel/Gasoline fats, waste oils, or virgin oils blended with crude oil as a feedstock for making low-sulfur diesel/gasoline in petroleum refinery Pyrolysis Liquids as a boiler fuel or an alternative feedstock to petroleum refinery or gasification facility, also a future source of aromatics and/or phenols Synthesis Gas for conversion to Fischer Tropsch liquids, MeOH/DME, or mixed alcohols Algae as alternative source of triglycerides for biodiesel or green diesel

Long Term

Hydrocarbons from hydrogenation of carbohydrates or lignin

Microalgae as a Source of Biofuels

DOEs Aquatic Species Program at NREL (1978-96) provided the technical foundation for producing biodiesel from algae The concept involves produce biofuels from:
Sunlight CO2 in fuel gases and/or vent gases Unproductive land Brackish or saline water

Productivity per acre potential (~10,000 gal/acre/yr) far exceeds terrestrial plants R&D is needed to reach this potential! NREL and industry exploring use of algal oils in existing refineries Algal carbohydrates can be integrated into ethanol production

Diesel/Jet Fuel From Algae

Low Land Use Required for Algal Biofuels

(Basis: algal oil needed for 5 Billion gal/yr Jet Fuel)
Near Term: with current state of the art 4,000,000 acres (6,500 square miles) Longer Term: with targeted research plan 530,000 acres (830 square miles)

Arizona: 73 million acres 114,000 sq. mi.

Summary & Conclusions

Biofuels are the only renewable option for liquid transportation fuels Resource is sufficient to supply a large portion of demand today, with potential to expand in the future Ethanol and biodiesel are the best near-term options for deployment must transition to cellulosic biomass On-going R&D may create other biofuel options in the future Different biofuel options offer a mix of pros and cons

Illustration by Oak Ridge National Lab