Production fuel from cellulosic biomass

Ri k G t fRick GustafsonSchool of Forest Resources 22 October 2009

Motivation for biofuelsMotivation for biofuelsClimate Change

Biomass is renewable and can be carbon neutral

Cellulosic ethanolCorn ethanol

Source: National Geographic

Motivation for biofuelsMotivation for biofuels

Economic utilizationEconomic utilization of waste biomass

Motivation for biofuelsMotivation for biofuels

Energy Independence

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

Motivation for biofuelsMotivation for biofuelsExpensive 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 iGulf of MexicoNY 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 andFigure 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 RFSCurrent Ethanol Production2007 RFS - Conventional2007 RFS - Cellulosic Biofuels2007 RFS - Biomass-based Diesel2007 RFS - Unaffiliated

20

25

Billio

n G

allo

ns p

er

Cellulosic

10

15

Ren

ewab

le F

uel (

B

mat

ed

0

5

R

Estim

Corn

02000 2005 2010 2015 2020

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

U.S. Biomass Resource AssessmentU 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 whenThe  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 ll18 million tons of biomass available annuallyAssume 90 gallons fuel/ton biomassTotal biofuel = 1,620,000,000 gallons/year

Total WA oil consumption = 6 500 000 000 gallons/year6,500,000,000 gallons/year

Range of Biorefinery ConceptsRange of Biorefinery Concepts

UUC iC iBiBi UsesUsesFuels

EthanolRenewable DieselMi d Al h l

Conversion ProcessesConversion Processes

Biomass FeedstockBiomass Feedstock

Mixed AlcoholsDimethyl Ether

PowerElectricityHeat

ChemicalsPlasticsSolventsChemical IntermediatesPhenolics

Enzymatic FermentationGas/liquid Fermentation

TreesGrasses

AdhesivesFurfuralFatty AcidsAcetic AcidCarbon BlackEt

Acid Hydrolysis/FermentationGasificationPyrolysis

Agricultural CropsResiduesAnimal WastesM i i l S lid W t

10/29/2009 17

Etc.Food and Feed

PyrolysisCombustionCo-firing

Municipal Solid Waste

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

What is biomass made of?Representation of Cell Wall Components

Cellulose

Hemicelluloses

LigninLignin

Cellulose For Chemists• Very long straight chain polymer of glucose:  approximately 

10 000 in a row in wood Cotton is nearly pure cellulose10,000 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

OHHO

OHHO

CH2OHOH

CH2OH

HO

OH

CH2OH

HO

O

β

ββ

β

2ββ

Cellulose

Hemicelluloses for ChemistsHemicelluloses for Chemists• Branched little uncolored sugar polymers (~ 50 to g p y (300 sugar units)– Composition varies between wood species

• 5 carbon sugars: xylose, arabinose5 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 OO

O

OOHHO HO OH

OO

OO

OHHO OO

HO OH

O

O

CO2HH3CO OHHOH2C

O

O

CO2HOH

Lignin for Chemists

OHOCH3 CH3

CHCH

H2COH

16

H2COHCH2

CH2

H C26

CH

28

27

O

CH2OHH

CH3

CH

O

O

H2COH

H3COOCH3

COHHHC

CH2OH

OH CH2OHCO

H3CO

CH

6

OCH3

OO

C

CHO

H3C

H

CH3

CH

OHOH3C

15

16

Carbohydrate

CH2OH

OH

OCH3

HC 14

O

C O

OCH3

24

25 H2COHHH3CO

CH

CHO

O

C O

CH

H

CH

CHOH2

HOOCH3

OH4

5 7

HHC CH

CH2O

C

CHO

H2C

8

HO

CH2OHH3C13

O

CH

O CH

O

H2COHHC

CHO

24

H2COH

OHCH

23

COH

OCHCHHOH

CH

C

OH2C

CHO

O CH2OHH3C

2

3O

O CHH3C

8

OHC CH CH2OH

CH2OH

OOH3C

9

10

H3C12 CHO

17

HOCHO

OH C

O

OCH

CH

O

COHH2CH

H2COH

OCH3

C

CHCHCHO

22

OCH3

C O

O

O CH

H3CCH2OH

1

C

OH10

OHC CH

COHH2

CH2O

CH

11

O

C O CH2

H3C18

HCHO

O

H

H3C

19COHHCOHH2

H O

HC O

C

OCH3

21

CH2 O

COHHHCOH

OOH

H3C

OHOCH3

20

Chemical compositionChemical composition

Feedstock Glucan (cellulose) (%) Xylan (hemicellulose) (%) Lignin (%)

Corn stover 37.5 22.4 17.6

Corn fiber 14 3 16 8 8 4Corn fiber 14.3 16.8 8.4

Pine wood 46.4 8.8 29.4

Poplar 49.9 17.4 18.1p

Wheat straw 38.2 21.2 23.4

Switchgrass 31.0 20.4 17.6g

Chemical composition of biomass (adapted from Mosier et al., 2005).

Approaches to cellulosic biofuels

EthanolEthanol

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

Bioconversion of biomass to 

Liquid Sugars Eth l

ethanol (hydrolysis)

Pretreatment

qphase Sugars Ethanol

Fermentation

BiomassLignin

RSolid phaseCellulose

Recovery

FermentationHydrolysis

EthanolSugars

PretreatmentPretreatment

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

Various pretreatment methodsVarious pretreatment methodsIncreases 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., 2005Minor effect Major effect

Bioconversion of biomass to 

Liquid Sugars Eth l

ethanol (hydrolysis)

Pretreatment

qphase Sugars Ethanol

Fermentation

BiomassLignin

RSolid phaseCellulose

Recovery

FermentationHydrolysis

EthanolSugars

E y e Fu tioEnzyme FunctionThere are a large number of fungal enzymesThere 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 cellobiosesuccessively cleaving off the disaccharide cellobiose.

» Beta‐glucosidase (or cellobiase) which cleaves cellobiose to two glucose units. 

CellulasesCellulases

Binding domain Catalytic domainBinding 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

FermentationFermentationDefined as:Cellular metabolism under anaerobic conditions for the production of energy and metabolic intermediatesMany organisms can “ferment” (i e growMany organisms can  ferment  (i.e., grow anaerobically)Not all produce ethanol as an end‐product of p pfermentation» Butanol» Acetic acid» Acetic acid» Propionic acid» Lactic acid

Pyrolysis

Thermoconversion - Basic Definitionsy 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 productp 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 StepsMajor 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&

Powery 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 temperatureshort residence timeshort residence time

GASIFICATION 5% 10% 85%high temperaturelong residence time

34

Source: Bridgewater and Czernik

Primary Energy Source Syngas Step Conversion Technology Products

Fischer Tropsch

(FT)Upgrading Naphtha

DieselSyngas to Liquids (GTL) ProcessNatural

Gas(FT)

Lubes

Syngas to Chemicals TechnologiesCoal

Syngas(CO + H2)

Syngas to Chemicals Technologies

M th l

Acetic Acid

MethanolBiomass

Hydrogen

Mixed Alcohols (e.g. ethanol, propanol)

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

Extra Heavy

Oil

10/29/2009 35Source: BP

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

• Thermal decomposition occurring in the absence of oxygenabsence 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 organic chemicals. 

• Dark brown mobile liquidCombustible• 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 37Source: Bridgewater and Czernik

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

B io-o il

Extract

Bo ile r U pgrade

H eat Chemicals

10/29/2009 38E lectric ity T ransport fue l Source: Bridgewater and Czernik

Potential for mobile unit

Forest

Upgrade biooil at refineryForest Residuals

BioOilPyrolysis

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

39FOREST

biomass because of higher energy density

Yields & Carbon UtilizationCellulosic

( C)Cellulosic

( C)Cellulosic

( C)Ethanol Corn Ethanol

SPyrolysis

OMethanol

Ethanol (BC) Ethanol (TC) Steam

Ethanol (TC) POX

Dry Mill SugarCane

Fuel OilIntermediate

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 115B P d tBy-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 3.11Process Efficency, HHV Overall (Prod + Byprod) % 48 47 46 74 68 55 Product % 44 40 37 44 67 55Carbon Utilization (basis feed carbon)Carbon Utilization (basis - feed carbon) Product % 31 27 26 39 59 35 By-Product % -- 6 5 37 -- 0 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 Prices100 MMGPY EtOH Production, $2005$

10/29/2009 41

Geographic, Feedstock, and Technology DiversityMajor DOE Biofuels Project Locations

RSE Pulp & Chemical, LLCBi h i l

DOE Great LakesNewPage

Thermochemical

MascomaBiochemical

Various (Lebanon, NH)

Cargill IncBiochemical

Various(Minneapolis, MN)

Regents of the University of Minnesota

Various(Minneapolis, MN)

Cornell University(I h NY)

BiochemicalWoody Biomass-

Mill Residues(Old Town, ME)

MascomaBiochemicalHardwoods

(Upper Peninsula, MI)Flambeau RiverThermochemical

Forest Residues/Wood Waste(Park Falls, WI)

Pacific EthanolBiochemical

Wheat Straw, Stover, Poplar Residues(Boardman, OR) Montana State University

Bozeman, (MT)

University of Maine(Orono, ME)

University of M h A h

PoetBiochemical

Corn Cob/Corn Fiber(Emmetsburg, IA)

DOE Joint Bioenergy Institute(Berkeley, CA)

DOE Great Lakes Bioenergy Research Center

(Madison, WI)

ThermochemicalWoody Biomass – Mill Residues

(Wisconsin Rapids, WI)

DSM Innovation CenterBiochemical

Various(Parsippany, NJ)

NovozymesBiochemical

Various

Purdue University(West Lafayette, IN)

(Ithaca, NY)

GE Global Research(Niskayuna, NY)

Emery Energy

Gas Technology Institute (Des Plaines, IL)

UOP, LLCThermochemical(Des Plaines, IL)

Stevens Institute of Technology

(Hoboken NJ)Univeristy of

Toledo(Toldeo, OH)

Massachusetts – Amhers(Amherst, MA)

BlueFire EthanolBiochemical

Municipal Solid Waste(M CA)

Lignol Biochemical

Woody Biomass- Ag Residues

(Grand Junction, CO) ICMBiochemical

Switchgrass, Forage Sorghum, Stover(St. Joseph, MO)

AbengoaBiochemica

Agricultural Residue(Hugoton, KS)

DOE Bioenergy Science Center

(Oak Ridge, TN)

(Davis, CA)Genencor

BiochemicalVarious

(Palo Alto, CA)

Dupont Biochemical

Various(Wilmington, DE)

Purdue UniversityBiochemical

(West Lafayette, IN)

Ceres, IncVarious

(Thousand Oaks CA)

AlltechBiochemical

Corn Cobs/Corn Fiber(Washington County, KY)

Emery EnergyThermochemical

Corn Stover(Salt Lake City, UT)

Iowa State (3)University(Ames, IA)

Research Triangle Institute (2)ThermochemicalWoody Biomass

(Research Triangle Park, NC)University of Georgia(Ath GA)

( , )

Virginia Tech(Blacksburg, VA)

(Mecca, CA)

Range FuelsThermochemical

Woody Waste(Soperton, GA)

Verenium CorpBiochemical

Various (San Diego, CA)

Nine Small-Scale Biorefinery Projects

(Thousand Oaks, CA)Southern Research

InstituteThermochemical

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 pSouth Dakota State Univ., Brookings, SD

Cornell University, Ithaca, NYUniv. of Tennessee, Knoxville, TN

Oklahoma State Univ., Stillwater, OKOregon 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