biomass conversion opportunities & options · biochemical conversion existing distribution...

NREL is a national laboratory of the U.S. Department of Energy Office of Energy Efficiency and Renewable Energy operated by the Alliance for Sustainable Energy, LLC

Hawaii HCEI/DBEDT Biomass/ Biofuels Training Program

John Ashworth and Scott Turn April 10, 2012

Biomass Conversion Opportunities & Options

Transportation Fuels

National Renewable Energy Laboratory Innovation for Our Energy Future


Ethanol is the Most Mature Biofuel Technology

U.S. Biomass Resource Assessment

Baseline Case

High Yield Case

Over 1 billion tons of biomass could be available annually in the future at $60/dry ton or less


Significance of the “Billion Ton” Scenario

Billion Barrel of Oil Equivalents


Primary Biomass Conversion Routes to Liquid Fuels

Transformation through Intermediates (sugars)

“Biochemical conversion”

“Thermochemical conversion”

Gasification (reduction to CO, H2) and Pyrolysis

Biomass Feedstocks

Lignocellulosic Biomass (wood, agri, waste, grasses, etc.)

Sugar/Starch Crops (corn, sugar cane, etc.)

Natural Oils (plants, algae)

Ag residues, (stover, bagasse)

Intermediates

Syn Gas

Bio-Oils

Lignin

Sugars

Gasification

Pyrolysis & Liquefaction

Hydrolysis

* Blending Products

Transportation Fuels Ethanol &

Mixed Alcohols

Diesel*

Methanol

Gasoline*

Diesel*

Gasoline* & Diesel*

Diesel*

Gasoline*

Hydrogen

Ethanol, Butanol, Hydrocarbons

Biodiesel

Green diesel

Catalytic synthesis

FT synthesis

MeOH synthesis

HydroCracking/Treating

APP

Catalytic pyrolysis

APR

Fermentation

Catalytic upgrading

MTG

Transesterification

Hydrodeoxygenation

Fermentation

Biofuels Transportation Options

7

Transportation Fuels –

Biochemical Routes


Biomass Feedstocks





Intermediates

Syn Gas

Bio-Oils

Lignin

Sugars

Gasification


Hydrolysis

* Blending Products


Mixed Alcohols

Diesel*

Methanol

Gasoline*

Diesel*

Gasoline* & Diesel*

Diesel*

Gasoline*

Hydrogen


Biodiesel

Green diesel

Catalytic synthesis

FT synthesis

MeOH synthesis


APP

Catalytic pyrolysis

APR

Fermentation

Catalytic upgrading

MTG

Transesterification

Hydrodeoxygenation

Fermentation

Biofuels Transportation Options

9


Near-Term Focus on Ethanol

Ethanol – as a blending agent from either grain or cellulosic material from Agriculture 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

Hydrocarbons – from hydrogenation of carbohydrates or lignin Long Term

Near Term

NATIONAL RENEWABLE ENERGY LABORATORY Innovation for Our Energy Future

Current Biofuels Status Biodiesel – 173 Companies; 1.1 billion gallons of production (2011), 2.69 billion gallons/yr capacity Corn ethanol2

• 209 commercial plants operating • 13.9 billion gal/yr. production (2011) • Additional 1-2 billion gal/yr shut-in, planned or

under construction Cellulosic ethanol (current technology)

• Projected commercial cost ~$2.50 /gallon

Updated January 2012 Sources: 1- National Biodiesel Board, 2 - Renewable Fuels Association, all other information based on DOE and USDA sources

NREL Research Thrusts • The biorefinery and cellulosic ethanol • Solutions to under-utilized waste residues • Energy crops

Key DOE Goals • 2012 goal: cellulosic ethanol $2.15/ETOH gallon • 2022 goal: 36B gal Renewable Fuel; 21B gal “Advanced Renewable

Fuel”– 2007 Energy Independence and Security Act • 2030 goal: 60 billion gal ethanol (30% of 2004 gasoline)

11


The Problem Corn Prices and Ethanol Prices are Decoupled – the Example of 2006

$0.00

$0.50

$1.00

$1.50

$2.00

$2.50

$3.00

$3.50

$4.00

Jan

FebMarc

hApr

ilMay

Ju

ne Ju

lyAug

Sept

Oct Nov Dec

($/g

allo

n or

$/b

ushe

l)

Corn Prices Ethanol Production Cost (Nat Gas $4)Ethanol Production Cost (Nat Gas $7) Gasoline Rack PriceEthanol Contract Prices


We Must Transition to Cellulosic Biomass

Today & Near Term

Corn Ethanol

Biochemical Conversion

Existing Distribution

Infrastructure

2012 and Beyond

Agricultural residues,

energy crops, natural oils,

wood/forestry resources

Cellulosic Ethanol Advanced

Biochemical Conversion

and

Thermochemical Conversion

Expanded, Advanced

Distribution Infrastructure

Cellulosic ethanol will help meet future biofuels demand


Biomass Fractionation in Pretreatment


Pretreatment

• Converts hemicellulose to fermentable sugars

• Makes cellulose susceptible to enzymatic hydrolysis


Conversion of Biomass

100 g raw solids (dry) feedstock

27 g residue solids (dry)

lignin co-product

60 g pretreated solids (dry)

cellulose + lignin


Enzymatic Hydrolysis Research

NREL worked with Genencor and Novozymes for 4 years • Focusing on enzyme

biochemistry, cost, and specific activity

• Investigating the interaction of biomass pretreatment and enzymatic hydrolysis

Result • 20-fold reduction in cost

contributions of enzymes

($/gal ethanol)

E1 from A. cellulotiticus CBH1 from T. reesei

$40 million R&D effort cost-shared by the Office of the Biomass Program and the enzyme manufacturers


Fermentation

Development of Zymomonas

Introduced xylose utilization - 1994

Introduced arabinose utilization - 1995

Combined pentose utilization - 1997

Stabilization by integration - 1999

Further Development in CRADA with DuPont 2002-2007

$0.00

$1.00

$2.00

$3.00

$4.00

$5.00

$6.00

$7.00

$8.00

$9.00

$10.00

2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012

Min

imum

Eth

anol

Sel

ling

Pric

e (2

007$

per

gal

lon)

Conversion Feedstock

$3.85 $3.64 $3.57

$3.18 $2.77

$2.56 $2.15

$4.27

$5.33

$6.90

$9.16

Bench Scale - Enzymes

Scale Up Pretreatment

Scale Up Saccharification

BC Conversion to Cellulosic Ethanol Historic State of Technology

Significant Cost Reduction of Cellulosic Ethanol Resulting from R&D

Butanol (n, iso)

Industrial Participants: Butamax (DuPont, BP), Tetravitae (now Eastman), Gevo, Cobalt, Butylfuel – Green Biologics, etc

Advantages (compared to ethanol): • Higher energy content, • More compatible with existing infrastructure • Multiple higher-value markets, valuable platform intermediate for fuels (gasoline, jet)

and commodity chemicals Disadvantages / Technical Challenges (in comparison to ethanol): • Toxicity • Yield Demonstrated largely on conventional feedstocks (corn starch, sugar) and

less on biomass-derived sugars

Advanced biofuels from sugar

Starch

Sugar

Aqueous-Phase Reforming

Fermentation with engineered microbes

Sugarcane

Dark Algae Oil

Cellulosics

Fermentation

LS9, Amyris Solazyme

Gasoline

Diesel

Jet

Virent

Gasoline

Diesel

Jet

Biodiesel

Ethanol

Diesel

Benefits •Infrastructure-compatible •Highly controlled fuel properties

Challenges •Feedstock availability •Compatibility with cellulosic sugar •Lower yields (compared to ethanol), higher costs

Transportation Fuels –

Thermochemical Routes


Biomass Feedstocks





Intermediates

Syn Gas

Bio-Oils

Lignin

Sugars

Gasification


Hydrolysis

* Blending Products


Mixed Alcohols

Diesel*

Methanol

Gasoline*

Diesel*

Gasoline* & Diesel*

Diesel*

Gasoline*

Hydrogen


Biodiesel

Green diesel

Catalytic synthesis

FT synthesis

MeOH synthesis


APP

Catalytic pyrolysis

APR

Fermentation

Catalytic upgrading

MTG

Transesterification

Hydrodeoxygenation

Fermentation

Biofuels Transportation Thermochemical Options

23


Other Near-Term Biofuel Technologies

Long Term

Near Term


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

•Roughly 2 billion gallon per year resource – Market demand is leading to

increased grease collection – Potential for new oil-seed crops or

increased oil content in conventional crops

– Corn oil recovery from ethanol production

– Longer-term, algae may provide a large feedstock resource

•Renewable Fuel Standard mandates 1 billion gallon market in 2012

•More than 1.1 billion gallons produced in U.S. in 2011

Market Status of Biodiesel

Mon

thly

Pro

duct

ion,

Mill

ion

Gal

lons

0

20

40

60

80

100

20012002

20032004

20052006

20072008

20092010

Record volume in May 2011

• Mature ASTM specification eliminates performance problems seen in the past

• 90+% of production volume meets ASTM requirements

– 80% of production today is from BQ-9000 companies – Ensures B100 meets ASTM quality requirements

Performance of Biodiesel

•Modern emission controls largely eliminate fuel effects on emissions

No biodiesel effect on NOx, even for B100 in some tests

•Ongoing research to ensure no effect on catalyst durability

•B20 had impact on fuel economy for this car

2010 VW Jetta – 2.0L TDI, DOC+DPF+LNT, Tier II Bin 5


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

• 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

Catalytic Cracker

Distillate Hydrotreater

Oils and Greases

Green Gasoline & Olefins

Green Diesel

ISBL Petroleum Refinery

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

Market Status of Renewable Diesel •Commercial production in US from poultry fat at one location

– 70 million gal/year capacity – Meets ASTM specification for diesel fuel (D975) – Hydrocarbon with very low oxygen, sulfur, and other impurities – High cetane number – Cloud point can be varied seasonally

•Pilot scale production from sugar (via biochemical route) – Product is a single hydrocarbon compound – Excellent diesel fuel properties – Very low freezing point, potential use as jet fuel

•Smaller scale production from sugar (catalytic reforming) and biomass (fast pyrolysis/hydrotreating)

– We have not yet been able to test these materials

28

Performance of Renewable Diesel

29

• High cetane number and low aromatic content cause reduction in formation of NOx and fine particles

• High purity materials: • No impact on catalyst durability • Require additives for lubricity,

conductivity, and corrosion protection – as does conventional diesel

• Will typically be used as a blend component because of high quality

• Small reduction in fuel economy in some engines

• Lower btu/gal than petroleum diesel

A RD20 A RD100 B RD20 B RD35 D RD20 D RD100

NO

x, Pe

rcen

t Cha

nge

Rel

ativ

e to

ULS

DH

DD

T C

ycle

-12

-10

-8

-6

-4

-2

0

2

2008 Pickup Truck Engine, DOC-DPF, HD engine certification


Mid-Term Biofuel Technologies

Long Term

Near Term




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


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

Bio-oil is comprised of many oxygenated organic chemicals, with water-miscible and oil-miscible fractions

Based on research at NREL (1990 - 2006)

• 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 odor

• “Ages” – viscosity increases with time



Long Term

Near Term Ethanol – as a blending agent from either grain or cellulosic

material from Agriculture 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 mixed alcohols, Fischer Tropsch liquids, MeOH, or DME


Gasification Offers Many Feed & Product Options

Primary Energy Source Syngas Step Conversion Technology Products

Syngas(CO + H2)

Fischer Tropsch

(FT)Upgrading

Lubes

Naphtha

DieselSyngas to Liquids (GTL) Process

Mixed Alcohols (e.g. ethanol, propanol)

Syngas to Chemicals Technologies

Methanol

Acetic Acid

Others (e.g. Triptane, DME, etc)

Coal

Natural Gas

Biomass

Hydrogen

Extra Heavy

Oil

Slide courtesy of BP Corporation

Methanol

Advanced biofuels from synthesis gas

Syngas gasification

Fischer-Tropsch Synthesis

Methanol Synthesis

Fermentation

Dry Organic Material

Cellulosics

Mixed Alcohol Synthesis

Gasoline

Diesel

Jet

Solena, Choren Gasoline

Ethanol

Propanol+

Methanol-to- Gasoline Ethanol

Coskata, INEOS

Benefits •Product versatility •Proven technology

Challenges •Biomass collection radius dictates smallish plant size •Limited economy of scale

NREL is a national laboratory of the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, operated by the Alliance for Sustainable Energy, LLC.

National Advanced Biofuels Consortium

Project Objective – Develop cost-effective technologies that supplement petroleum-derived fuels with advanced “drop-in” biofuels that are compatible with today’s transportation infrastructure and are produced in a sustainable manner.

ARRA Funded: - 3 year effort - DOE Funding $35.0M - Cost Share $12.5M Total $47.5M

Consortium Leads National Renewable Energy Laboratory Pacific Northwest National Laboratory Consortium Partners Albemarle Corporation Amyris Biotechnologies Argonne National Laboratory BP Products North America Inc. Catchlight Energy, LLC Colorado School of Mines Iowa State University Los Alamos National Laboratory

Pall Corporation RTI International Tesoro Companies Inc. University of California, Davis UOP, LLC Virent Energy Systems Washington State University

35

Biomass Refinery-Ready Intermediates Finished Fuels and Blendstocks

Existing Refinery Infrastructure

Atm

osph

eric

and

Va

cuum

Dis

tilla

tion

Gas

L Naphtha

H Naphtha

LGO

VGO

Atm. Res.

Vac. Res.

Reform

FCC

Alky/Poly

HT/HC

Coker

Gasoline Jet Fuel Diesel Fuel

Crude Oil

Insertion Point #1:

Insertion Point #3:

Insertion Point #2:

Integration With Existing Fuels Infrastructure

36

National Advanced Biofuels Consortium (NABC), www.nabcprojects.org



Long Term

Near Term




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 mixed alcohols, Fischer Tropsch liquids, methanol, or dimethyl ether

Algae to Fuels – either to biodiesel or as a lipid source for green diesel or synthetic gasoline

Hydrocarbons – from hydrogenation of carbohydrates or lignin


A Novel Approach for Making Jet Fuel from Biomass

Combine two technologies: Algae & Green Diesel

CO2

Cultivation Ponds

Microalgae

• Ethanol • Power • Food

60% Triglyceride

40% Carbohydrates

and Protein

Jet Fuel (JP-8)

Green Diesel


Thank you for the opportunity.

Are there any questions?

biomass conversion opportunities & options · biochemical conversion existing distribution...

Documents