Production fuel from cellulosic biomass Ri k G Rick Gustafson t f - - PowerPoint PPT Presentation

Production fuel from cellulosic biomass

Ri k G t f Rick Gustafson School of Forest Resources

22 October 2009

Motivation for biofuels Motivation for biofuels

Climate Change

Biomass is renewable and can be carbon neutral

Cellulosic ethanol Corn ethanol

Source: National Geographic

Motivation for biofuels Motivation for biofuels

Economic utilization Economic utilization

• f waste biomass

Motivation for biofuels Motivation for biofuels

Energy Independence

http://www.nationmaster.com/red/graph/ene_oil_exp_net-energy-oil-exports-net&b_map=1#

Motivation for biofuels Motivation for biofuels

Expensive oil? Running out of oil?

‘Peak Oil’ Is a Waste of Energy – NY Times 24 August 2009

BP Finds Giant Oil Field Deep in G lf f M i Gulf of Mexico NY Times 2 Sept. 2009

Washington State ‐ Climate change mitigation

Fires 33.5 M mt/2006

Figure 4 4 2 Washington historic CO2e emissions by sector with fire emissions superimposed (adapted from Waterman-Hoey and Figure 4.4.2. Washington historic CO2e emissions by sector with fire emissions superimposed (adapted from Waterman-Hoey and Nothstein 2007, Wiedinmyer and Neff 2007).

Climate change mitigation: CO2 emission goals relative to current emissions

WA GHG Reduction Goals 2020 to 1990 2050 to 50% 1990 2035 to 75% 1990 2050 to 50% 1990

Waterman‐Hoey and Nothstein. 2007. Washington’s Greenhouse Gas Emissions: Sources and Trends ‐ 2006. WA Dept. of Community, Trade and Economic Development. Olympia, WA. 18 pp. http://www.cted.wa.gov/site/853/default.aspx

Current Market Overview

Current ethanol capacity = 10.6 billion gal/year Current biodiesel capacity = 700 million gal/year

Source: http://www.ethanolrfa.org/industry/statistics,

Ethanol futures, $/gal

Energy Independence and Security Act 2007 (Now they are talking about 60 billion gals/year!!!!) (Now they are talking about 60 billion gals/year!!!!)

40 30 35 Year)

2005 EPAct RFS Current Ethanol Production 2007 RFS - Conventional 2007 RFS - Cellulosic Biofuels 2007 RFS - Biomass-based Diesel 2007 RFS - Unaffiliated

20 25 Billion Gallons per

Cellulosic

10 15 Renewable Fuel (B mated 5 R Estim

Corn

2000 2005 2010 2015 2020

Total US oil consumption = 320 billion gals/year Total US oil imports = 220 billion gals/year

U.S. Biomass Resource Assessment

U d t d t A il 2005

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

13

• Current biomass production less than 500 million tons/year

The “Billion Ton” potential represents about 1/3 of our petroleum use when The Billion Ton potential represents about 1/3 of our petroleum use when converted to liquid fuels 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

Washington State situation is different

Source: WSU, WA DOE. http://www.ecy.wa.gov/pubs/0507047.pdf

Replace oil with biofuels in Washington State??? 18 illi t f bi il bl ll 18 million tons of biomass available annually Assume 90 gallons fuel/ton biomass Total biofuel = 1,620,000,000 gallons/year Total WA oil consumption = 6 500 000 000 gallons/year 6,500,000,000 gallons/year

Range of Biorefinery Concepts Range of Biorefinery Concepts

U C i C i Bi Bi Uses Uses

Fuels Ethanol Renewable Diesel Mi d Al h l

Conversion Processes Conversion Processes Biomass Feedstock Biomass Feedstock

Mixed Alcohols Dimethyl Ether Power Electricity Heat Chemicals Plastics Solvents Chemical Intermediates Phenolics

Enzymatic Fermentation Gas/liquid Fermentation Trees Grasses

Adhesives Furfural Fatty Acids Acetic Acid Carbon Black Et

Acid Hydrolysis/ Fermentation Gasification Pyrolysis Agricultural Crops Residues Animal Wastes M i i l S lid W t

10/29/2009 17

Etc. Food and Feed

Pyrolysis Combustion Co-firing Municipal Solid Waste

Adapted from Holmgren etal (2008); Hydrocarbon Processing, Sep.

What is biomass made of?

Representation of Cell Wall Components

Cellulose Hemicelluloses Lignin Lignin

Cellulose For Chemists

• Very long straight chain polymer of glucose: approximately

10 000 in a row in wood Cotton is nearly pure cellulose 10,000 in a row in wood. Cotton is nearly pure cellulose.

• Cellulose molecules link up in bundles and bundles of bundles

and bundles of bundles of bundles to make fibers

• Cellulose forms tight bundles which are very resistant to

chemical attack

Cellobiose Unit

O O O O O O O O

CH2OH OH HO OH HO CH2OH OH CH2OH HO OH CH2OH HO O β β β β

2

β β

Cellulose

Hemicelluloses for Chemists Hemicelluloses for Chemists

• Branched little uncolored sugar polymers (~ 50 to

g p y ( 300 sugar units)

– Composition varies between wood species

• 5 carbon sugars: xylose, arabinose

5 ca bo suga s: y ose, a ab ose

• 6 carbon sugars: mannose, galactose, glucose
• Uronic Acids: galacturonic acid, glucuronic acid
• Acetyl and methoxyl groups (acetic acid & methanol)

O O O O O

OH HO HO OH

O O O O

OH HO

O O

HO OH

O O CO2H H3CO OH HOH2C O O CO2H OH

Lignin for Chemists

OH OCH3 CH3 CH CH H2COH 16 H2COH CH2 CH2 H C 26 CH 28 27 O CH2OH H CH3 CH O O H2COH H3CO OCH3 COH H HC CH2OH OH CH2OH C O H3CO CH 6 OCH3 O O C CH O H3C H CH3 CH OH O H3C 15 16 Carbohydrate CH2OH OH OCH3 HC 14 O C O OCH3 24 25 H2COH H H3CO CH CH O O C O CH H C H C HOH2 HO OCH3 OH 4 5 7 H HC CH CH2 O C CH O H2C 8 HO CH2OH H3C 13 O CH O CH O H2COH HC CH O 24 H2COH O HC H 23 COH OCH CH HO H CH C O H2C CH O O CH2OH H3C 2 3 O O CH H3C 8 OHC CH CH2OH CH2OH O O H3C 9 10 H3C 12 CHO 17 HO CH O O H C O O CH CH O COH H2 C H H2COH OCH3 C CH CH CHO 22 OCH3 C O O O CH H3C CH2OH 1 C OH 10 O HC CH COH H2 CH2 O C H 11 O C O CH2 H3C 18 H CH O O H H3C 19 COH H COH H2 H O HC O C OCH3 21 C H2 O COH H HCOH O OH H3C OH OCH3 20

Chemical composition Chemical composition

Feedstock Glucan (cellulose) (%) Xylan (hemicellulose) (%) Lignin (%) Corn stover 37.5 22.4 17.6 Corn fiber 14 3 16 8 8 4 Corn fiber 14.3 16.8 8.4 Pine wood 46.4 8.8 29.4 Poplar 49.9 17.4 18.1 p Wheat straw 38.2 21.2 23.4 Switchgrass 31.0 20.4 17.6 g Chemical composition of biomass (adapted from Mosier et al., 2005).

Approaches to cellulosic biofuels

Ethanol Ethanol

J.A. Dumesic / Catalysis Today 111 (2006) 119–132

Bioconversion of biomass to

Liquid Sugars Eth l

ethanol (hydrolysis)

Pretreatment

q phase Sugars Ethanol

Fermentation

Biomass

Lignin R Solid phase Cellulose Recovery

Fermentation Hydrolysis

Ethanol Sugars

Pretreatment Pretreatment

Schematic of goals of pretreatment on lignocellulosic material (adapted from Hsu et al., 1980).

Various pretreatment methods Various pretreatment methods

Increases accessible surface area Decrystalizes cellulose Removes hemicellulose Removes lignin Alters lignin structure surface area

Uncatalyzed steam explosion ■ ■ Liquid hot water ■ ND ■ q pH controlled hot water ■ ND ■ ND Flow-through liquid ■ ND ■ hot water ■ ND ■ Dilute acid ■ ■ ■ Flow-through acid ■ ■ ■ AFEX ■ ■ ■ ■ ARP ■ ■ ■ ■ Lime ■ ND ■ ■ Adapted from Mosier et al., 2005

Minor effect Major effect

Bioconversion of biomass to

Liquid Sugars Eth l

ethanol (hydrolysis)

Pretreatment

q phase Sugars Ethanol

Fermentation

Biomass

Lignin R Solid phase Cellulose Recovery

Fermentation Hydrolysis

Ethanol Sugars

E y e Fu tio Enzyme Function

There are a large number of fungal enzymes There are a large number of fungal enzymes responsible for the breakdown of each wood

• component. Each enzyme plays specific roles:

E do beta 1 4 lu a a e a t ithi the hai b eaki it » Endo‐beta‐1,4‐glucanase acts within the chain, breaking it into smaller units and providing more ʺendsʺ for CBH. » Cellobiohydrolase (CBH), acts on the end of the molecule successively cleaving off the disaccharide cellobiose successively cleaving off the disaccharide cellobiose. » Beta‐glucosidase (or cellobiase) which cleaves cellobiose to two glucose units.

Cellulases Cellulases

Binding domain Catalytic domain Binding domain Catalytic domain

E d l

(EG)

Endoglucanases (EG)

cutting the cellulose chains randomly

Cellobiohydrolyses (CBH) cutting cellobiose units of the ends of the cellulose chains

Fermentation Fermentation

Defined as:

Cellular metabolism under anaerobic conditions for the production of energy and metabolic intermediates

Many organisms can “ferment” (i e grow Many organisms can ferment (i.e., grow anaerobically) Not all produce ethanol as an end‐product of p p fermentation

» Butanol » Acetic acid » Acetic acid » Propionic acid » Lactic acid

Pyrolysis

Thermoconversion - Basic Definitions

y y

• Thermal conversion (destruction) of organics in the absence of oxygen
• In the biomass community, this commonly refers to lower temperature thermal

processes producing liquids as the primary product p p g q p y p

• Possibility of chemical and food byproducts

Gasification

• Thermal conversion of organic materials at elevated temperature and

reducing conditions to produce primarily permanent gases, with char, water, and condensibles as minor products

• Primary categories are partial oxidation and indirect steam
• Primary categories are partial oxidation and indirect steam

10/29/2009 32

Biomass Conversion to Fuels – Major Biochemical Conversion Steps Major Biochemical Conversion Steps

Feed Processing and Handling

• Size Reduction
• Storage and Handling
• De-watering
• Drying

Gasification Pyrolysis Gas Cleanup High T Separation Gas Conditioning Collection/Fractionation Fuel Synthesis Upgrading Heat & Power y y Separation pg g

• Partial Oxidation
• Air blown

O bl

• Particulate removal
• Tar reforming
• Benzene removal
• Methane reforming
• CO2 removal
• H2/CO adjustment
• C1 chemistry

– FT liquids – MTG

• Oxygen blown
• Indirect
• Flash pyrolysis
• Steam pyrolysis
• Vacuum pyrolysis

Benzene removal

• S, N, Cl mitigation
• High T Filtration
• Alkali removal

H2/CO adjustment

• Sulfur polishing
• Aerosol collection
• Microfiltration
• Chemical Stabilization

MTG – Mixed OH

• Upgrading
• Production Separation

10/29/2009 33

• Hydrotreating
• Dehydration

Th di t ib ti f d t d d t t d id ti

Liquid Char Gas

The distribution of products depends on temperature and residence time

FAST PYROLYSIS 75% 12% 13% moderate temperature short residence time short residence time GASIFICATION 5% 10% 85% high temperature long residence time

34 Source: Bridgewater and Czernik

Primary Energy Source Syngas Step Conversion Technology Products

Fischer Tropsch (FT) Upgrading Naphtha Diesel

Syngas to Liquids (GTL) Process

Natural Gas

(FT) Lubes

Syngas to Chemicals Technologies

Coal Syngas (CO + H2)

Syngas to Chemicals Technologies

M th l Acetic Acid Methanol

Biomass

Hydrogen Mixed Alcohols (e.g. ethanol, propanol) Others (e.g. Triptane, DME, etc)

Extra Heavy Oil

10/29/2009 35 Source: BP

Pyrolysis is usually performed at lower temperature to produce a liquid biocrude.

• Thermal decomposition occurring in the

absence of oxygen absence of oxygen

• Is also the first step in combustion and

gasification processes

• Known as a technology for producing
• Known as a technology for producing

charcoal and chemicals for thousands years

10/29/2009 36

Biocrude is water miscible and is comprised of many oxygenated

• rganic chemicals.
• Dark brown mobile liquid

Combustible

• Combustible
• Not miscible with hydrocarbons
• Heating value ~ 17 MJ/kg

D it 1 2 k /l

• Density ~ 1.2 kg/l
• Acid, pH ~ 2.5
• Pungent odour

“ ”

• “Ages” ‐ viscosity increases with time

10/29/2009 37 Source: Bridgewater and Czernik

There are a number of applications for biocrudes There are a number of applications for biocrudes

Bio-oil Extract Boiler Upgrade Heat

Chemicals

10/29/2009 38

Electricity Transport fuel

Source: Bridgewater and Czernik

Potential for mobile unit

Forest

Upgrade biooil at refinery

Forest Residuals BioOil Pyrolysis

Much cheaper to ship biooil than biomass beca se of higher energ

39

FOREST biomass because of higher energy density

Yields & Carbon Utilization

Cellulosic ( C) Cellulosic ( C) Cellulosic ( C) Ethanol Corn Ethanol S Pyrolysis O Methanol Ethanol (BC) Ethanol (TC) Steam Ethanol (TC) POX Dry Mill Sugar Cane Fuel Oil Intermediate Intermediate

Yield

gal/ton biomass

90 80 77 102 12.3 137 149

gal Ethanol eq/ton biomass

90 80 77 102 12.3 135 115 B P d t By-Product

type

• C3+OH

C3+OH DDGS Sugar

• gal Ethanol eq/ton biomass
• 14

15 33 wt% 5.7 wt%

• Electricity, kWh/ton

196

• 26
• External Fuel

Nat Gas, MMBtu/dry ton

3.11 Process Efficency, HHV

Overall (Prod + Byprod) %

48 47 46 74 68 55

Product %

44 40 37 44 67 55 Carbon Utilization (basis feed carbon) Carbon Utilization (basis - feed carbon)

Product %

31 27 26 39 59 35

By-Product %

• 6

5 37

• Acid Gas/Fermentation CO2 %

16 15 24 19

• 0.3

Combustion Flue Gas CO2 %

53 52 36 5 41 47

Other % Type

char NG Flue Gas

%

8 10 18

Plant Gate Prices

100 MMGPY EtOH Production, $2005$

10/29/2009 41

Geographic, Feedstock, and Technology Diversity

Major DOE Biofuels Project Locations

RSE Pulp & Chemical, LLC Bi h i l DOE Great Lakes NewPage Thermochemical Mascoma Biochemical Various (Lebanon, NH) Cargill Inc Biochemical Various (Minneapolis, MN) Regents of the University of Minnesota Various (Minneapolis, MN) Cornell University (I h NY) Biochemical Woody Biomass- Mill Residues (Old Town, ME) Mascoma Biochemical Hardwoods (Upper Peninsula, MI) Flambeau River Thermochemical Forest Residues/Wood Waste (Park Falls, WI) Pacific Ethanol Biochemical Wheat Straw, Stover, Poplar Residues (Boardman, OR) Montana State University Bozeman, (MT) University of Maine (Orono, ME) University of M h A h Poet Biochemical Corn Cob/Corn Fiber (Emmetsburg, IA) DOE Joint Bioenergy Institute (Berkeley, CA) DOE Great Lakes Bioenergy Research Center (Madison, WI) Thermochemical Woody Biomass – Mill Residues (Wisconsin Rapids, WI) DSM Innovation Center Biochemical Various (Parsippany, NJ) Novozymes Biochemical Various Purdue University (West Lafayette, IN) (Ithaca, NY) GE Global Research (Niskayuna, NY) Emery Energy Gas Technology Institute (Des Plaines, IL) UOP, LLC Thermochemical (Des Plaines, IL) Stevens Institute of Technology (Hoboken NJ) Univeristy of Toledo (Toldeo, OH) Massachusetts – Amhers (Amherst, MA) BlueFire Ethanol Biochemical Municipal Solid Waste (M CA) Lignol Biochemical Woody Biomass- Ag Residues (Grand Junction, CO) ICM Biochemical Switchgrass, Forage Sorghum, Stover (St. Joseph, MO) Abengoa Biochemica Agricultural Residue (Hugoton, KS) DOE Bioenergy Science Center (Oak Ridge, TN) (Davis, CA) Genencor Biochemical Various (Palo Alto, CA) Dupont Biochemical Various (Wilmington, DE) Purdue University Biochemical (West Lafayette, IN) Ceres, Inc Various (Thousand Oaks CA) Alltech Biochemical Corn Cobs/Corn Fiber (Washington County, KY) Emery Energy Thermochemical Corn Stover (Salt Lake City, UT) Iowa State (3) University (Ames, IA) Research Triangle Institute (2) Thermochemical Woody Biomass (Research Triangle Park, NC) University of Georgia (Ath GA) ( , ) Virginia Tech (Blacksburg, VA) (Mecca, CA) Range Fuels Thermochemical Woody Waste (Soperton, GA) Verenium Corp Biochemical Various (San Diego, CA)

Nine Small-Scale Biorefinery Projects

(Thousand Oaks, CA) Southern Research Institute Thermochemical Various (Birmingham, AL) (Athens, GA) Georgia Tech (Atlanta, GA)

Regional Partnerships

Four Commercial-Scale Biorefinery Projects Four Improved Enzyme Projects Five Projects for Fermentation Organisms Five Thermochemical Syngas Projects Th Offi f S i Bi C t

Verenium Biofuels Corp. Biochemical Process Energy Cane and Bagasse (Jennings, LA)

g p

South Dakota State Univ., Brookings, SD Cornell University, Ithaca, NY

• Univ. of Tennessee, Knoxville, TN

Oklahoma State Univ., Stillwater, OK Oregon State Univ., Corvallis, OR Three Office of Science Bioenergy Centers DOE Joint Solicitation Biomass Projects Five Thermochemical Bio-Oil Projects Six University Projects Modified 10/1/2008