forest biorefineries transforming the forest products industry

Forest BioRefineriesTransforming the Forest

Products Industry

Arthur J. RagauskasInstitute of Paper Science and Technology

Georgia Institute of TechnologyChalmers University of Technology

Global ChallengesEnergy Needs

Terawatts Challenge-1940 2 TW-2004 15 TW

Biomass 1.6 TW

2050 ~30 – 60 TWBiomass 30 TW

2003 6.3 Billion People2050 8-10 Billion People

world population

0

2

4

6

8

10

1750 1800 1850 1900 1950 1998 2050

0

2,000

4,000

6,000

8,000

10,000

12,000

14,000

16,000

18,000

1971 1990 2004 2015 2030

OECD Transition Economies Developing Countries

Ener

gy D

eman

d (M

toe)

Stabilization of CO2 concentrations means fundamental change to the global energy system

Oil Oil + CCSNatural Gas Natural Gas + CCSCoal Coal + CCSBiomass Energy Nuclear EnergyNon-Biomass Renewable Energy End-use Energy

History and Reference Case

0

200

400

600

800

1000

1200

1400

1600

1850 1900 1950 2000 2050 2100

Glo

bal P

rimar

y E

nerg

y 18

50-2

100

(Exa

joul

es)

FutureHistory

Stabilization of CO2 at 550 ppm

0

200

400

600

800

1000

1200

1400

1600

1850 1900 1950 2000 2050 2100

Glo

bal P

rimar

y E

nerg

y 18

50-2

100

(Exa

joul

es)

.

FutureHistory

Preindustrial280ppm

Preindustrial280ppm

Source: Jae Edmonds

Decreasing U.S. Petroleum ConsumptionCongress:The “30 by 30” goal

World Ethanol and Biodiesel Annual Production

(Petroleum use @ 1150 B g/yr)

0

1

2

3

4

5

6

7

8

9

10

975

980

985

990

995

000

005

Fuel

(bill

ion

annu

al g

allo

ns)

EthanolBiodiesel

Energy Bill H.R.6:

• Replace 30% of gas and diesel consumption with biofuelsby 2030

• Requires approximately 1B dry tons of biomass for 60B gal using current technology

• “Billion Ton Study” – there is enough biomass in the US

• Decrease consumption by 18%in 14 years

• Grow production of renewable fuels to 31B gal/year by 2017

4359 4288

528251 79 79 40 32

0

500

1000

1500

2000

2500

3000

3500

4000

4500

Mill

ion

Ann

ual G

al

Braz

il

US

China EU Ind

iaCa

nada

Columbia

Others

Annual Ethanol Production by Country in 2005

Upper limit of corn ethanol is set to 15 billion gal per year (National Corn Growers Association)

With capacity being built we will reach this limit within two years

We must add cellulosic biofuels in order to meet our national goals

State of the Union Address

Potential Biomass Resource and Refinery Capacity in 2012: Logging

Residues, Crop Residues, Switchgrass

Source: Perlack et al., ORNL

Data do not include pulp & paper assets in the Southeast

Potential Biomass Resource and Refinery Capacity in 2030: Forest Residues (all),

Crop Residues, Switchgrass

Source: Perlack et al., ORNL

Data do not include pulp & paper assets in the SoutheastThe Southeast and Midwest will be the sources for US biomass

Cellulosic BioRefineries

Today- Tomorrow’s Forest Products BioRefiner

Current Products: Pulp, Tall Oil, TurpentineFuture Select Hemicellulose, Wood Extractives, Lignin

Material

Syngas Syngas Power Export 116 million BOE

or Liquid

Fuels/Chemicals109 million barrels

O2

PulpSW 55 million tons

Steam, Power& ChemicalsBL Gasifier

Wood Residual GasifierCombined Cycle SystemProcess to manufactureLiquid Fuels and Chemicals

Manufacturing

CO2

Extract Hemicellulosesnew productschemicals & polymers1.9 billion gallons Ethanol

600 million gallons Acetic Acid

Black Liquor& Residuals

The Forest Biorefinery – Production

•Add Fischer-Tropsch unit; convert BLG •Syngas to Renewable Fischer-Tropsch Fuel

BioRefinery: Hemicellulose Extraction

Experimental Pre-Extraction ConditionsLoblolly Pine Experimental Parameter

Alkaline Pre-extraction

Acidic Pre-extraction

Steam Pre-extraction

Temperature/ oC 100 - 170 130 - 150 130 - 170 Time/h 0.5, 1.0, 1.5 0.5, 1.0 0.5, 1.0, 1.5, 2.0 Chemicals/% 1.0, 1.5% NaOH 0.0, 0.2, 0.5% H2SO4 53 psi Ratio of Liquor to Wood

5.0 : 1.0 5.0 : 1.0 4.0 : 1.0

Post Extraction Washing

No Yes & No No

Acidic Pre-Extractions – Kraft Pulping

BioRefinery: Hemicellulose ExtractionAcidic Pre-Extracted Woodchips: Monosaccharide Analysis

Mass Terminal pH % Recovery

0.5h Pre-Extraction

0.0% H2SO4: 5 3.20.2% H2SO4: 5 2.70.5% H2SO4: 8 2.3

1.0h Pre-Extraction

0.0% H2SO4: 8 3.70.2% H2SO4: 10 2.40.5% H2SO4: 12 2.2

0

5

10

15

20

25

30

35

40

45

50% Hydrolyzed

Sugars

0 %H2SO4

0.2%H2SO4

0.5%H2SO4

0 %H2SO4

0.2%H2SO4

0.5%H2SO4

Arabinose

Galactose

Glucose

Xylose

Mannose

0.5 h 1.0 h

0 5.0 10.0 15.0 20.0 25.0 30.0 35.0Minutes

0

25

50

75

100

125

150

175

200

nC

1-2

Fuc os e

Arabinose

Galac tos e

Gluc ose

Xy los e

Mannose

Yields 10 – 18%


0

5

10

15

20

25

30

Kap

pa #

Control(

no pre-

extra

ction)

0.5hr

pre-extr

acted

/With

was

hing

0.0 %

H2SO4

0.2% H

2SO4

0.5% H

2SO4

1.0hr

pre-extr

acted

/With

was

hing

0.0 %

H2SO4

0.2% H

2SO4

0.5% H

2SO4

1.0hr

pre-extr

acted

/With

out w

ashin

g

0.0 %

H2SO4

0.2% H

2SO4

0.5% H

2SO4

Kraft Pulping Acidic Pre-Extracted Woodchips: Kappa #(Lignin Content

BioRefinery: Hemicellulose ExtractionKraft Pulping Acidic Pre-Extracted Woodchips: Viscosity

0.0

5.0

10.0

15.0

20.0

25.0

30.0

35.0

Visc

osity

/cP

Contro

l(no p

re-ex

tracti

on)

0.5hr

pre-ex

tracte

d/With

was

hing

0.0 %

H2S

O40.2

% H2S

O40.5

% H2S

O4

1.0hr

pre-ex

tracte

d/With

was

hing

0.0 %

H2S

O40.2

% H2S

O40.5

% H2S

O4

1.0hr

pre-ex

tracte

d/With

out w

ashin

g0.0

% H

2SO4

0.2% H

2SO4

0.5% H

2SO4

BioRefinery: Hemicellulose ExtractionKraft Pulping Acidic Pre-Extracted Woodchips: Burst

0.0

0.5

1.0

1.5

2.0

2.5Orig

inal

0.5hr

pre-ex

tracte

d(with

was

hing)

0 % H

2SO4

0.2% H

2SO4

0.5% H

2SO4

1.0hr

pre-ex

tracte

d(with

was

hing)

0 % H

2SO4

0.2% H

2SO4

0.5% H

2SO4

1.0hr

pre-ex

tracte

d(with

out w

ashin

g)0 %

H2S

O40.2

% H2S

O40.5

% H2S

O4

Burst Index

BioRefinery: Hemicellulose ExtractionAcidic Pre-Extracted Woodchips: Pretreatment Modification

Prior StudiesDirect H2SO4/H2O

t=0

H2SO4/H2Ot= 48 hSpray Chips 1 h, 150 oC

AlternativeApproachDelayed


H2SO4/H2O

Direct & Delayed

1 h, 150 oC

Reducing Sugars (mg/ml) % Hemicellulose0.5% H2SO4 Direct (t:0) 36.3 12Delayed (t: 48 h) 57.8 19

0.75% H2SO4 Direct (t:0) 67.9 22Delayed (t: 48 h) 72.2 23

Basic Pre-Extractions – Kraft Pulping


NaOH/H2O

1 h, 150 oCExp. Terminal pH %Sugar Recovery Reducing Sugar (mg/ml)150 oC 4.5% NaOH1.0 h: 10.6 8 1.9

160 oC 4.5%% NaOH1.0 h: 10.0 11 2.0

170 oC 4.5% NaOH, 2 h 8.9 11 2.36.0% NaOH, 1 h 11.3 14 2.59.0% NaOH, 1 h 12.7 16 3.312.0% NaOH, 1h 12.7 18 4.0

BioRefinery: Hemicellulose ExtractionKraft Pulping Alkali Pre-Extracted Woodchips: Kappa #

Experimental Conditions: NaOH: 4.5 – 12.0% t: 1.0 – 3.0 hrTemp.: 150 - 170 oC

0

10

20

30

40

50

60% Monosaccharide

150 C

NaOH 4.

5%, 1

hr

160 C

NaOH 4.

5%, 1

hr

170 C

NaOH 4.

5%, 1

hr

NaOH 4.

5%, 2

hr

NaOH 4.

5%, 3

hr

NaOH 6.

0%, 1

hr

NaOH 9.

0%, 1

hr

NaOH 12

.0%, 1

hr

ArabinoseGalactoseGlucoseXyloseMannose

Exp. Terminal pH150 oC 4.5% NaOH1.0 h: 10.6

160 oC 4.5%% NaOH1.0 h: 10.0

170 oC 4.5% NaOH, 1 h 9.14.5% NaOH, 2 h 8.94.5% NaOH, 3 h 8.06.0% NaOH, 1 h 11.39.0% NaOH, 1 h 12.712.0% NaOH, 1h 12.7


Benefits of Pre-extraction• Significant reliable source of Hemicelluloses• Improves pulpability• Benefits some bleaching operations

Concerns of Pre-extraction• Capital Costs - Partnership• Impact on strength properties

- Grade - Technology• Yield

- Technology - Data

OO

O OAcO

O

HOOAc

O

HOO

OO

AcOOH

O-XylanO

O

HOOAc

OO

AcOOAc

O

O

H3CO HO

OHHO2C O

HO

HOOH

Today- Tomorrow’s Forest Products TMP BioRefiner

Wood Debarking Collection Wood Chipping

Pulp Bleaching

Papermaking

Bark Energy

Wood

Chips

Pulping

WoodExtractives Sulfur Free

BiochemicalBioLube

Value-AddedChemicals

Glucomannans

- Strength Aid/Yield for Kraft- Clean Polysaccharide Resource

Current Products: PulpFuture Select Hemicellulose, Wood Extractives

Biorefinery: Mechanical PulpingCO2H

H

H

Abietic Acid

0.0%

0.5%

1.0%

1.5%

2.0%

2.5%

3.0%

0 7 14 21Day

Ace

tone

Ext

ract

ab

Ambient60oC, 80% RH45oC 73% RH

Filtrate Extractives

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

Chip wash Plug screwpressate

Reject screwpressate

Cloudy WW Central WW

mg/

ml

Fatty AcidsResin AcidsMonoglycerolSterolUnknown

Challenge: • Wood extractives cause process –

quality problemsPulp Extractives

0.00

0.20

0.40

0.60

0.80

1.00

1.20

1.40

1.60

1.80

Chips

1o R

efine

r2o

Refi

ner

Quenc

h Tan

k

1o Scr

een a

ccep

ts

1o S

creen

rejec

ts

Rej. Scr

een f

eed

Rej. Scr

een a

ccep

ts

TMP po

st re

finer

Y Blea

ched

pulp

PY Blea

ched

pulpGWD si

loPM H

eadb

ox

mg/

od g

Fatty AcidsResin AcidsAlkanolMonoglycerolSterolUnknown

Starting Chips 2.8%Pressure WashAcetone 70 oC 1.2%Ethyl alcohol 90 oC 1.2%0.2% Ethoxylates surfactant 90 oC 1.4%

TMP Woodchips Extractives

Biorefinery: Mechanical Pulping

OrginalAcetone Extracted

Ethanol Extracted

Aqueous Surfactant

Hexadecanoic acid

9,12-Octadecadienoic acid

Linolenic acid

Octadecanoic acid

11-Eicosaenoic acid

0

0.2

0.4

0.6

0.8

1

1.2

1.4

Hexadecanoic acid9,12-Octadecadienoic acidLinolenic acidOctadecanoic acid11-Eicosaenoic acid

mgr/gr od pulp

Fatty Acids


Resin Acids

0

1

2

3

4

5

6

7

8

9

Control TMP Acetoneextracted

TMP Ethyl alcoholextracted

TMP Surfactantpretreated

Tensile Index

Original


Resin Acids

50.5

51

51.5

52

52.5

53

53.5

54

54.5

55

55.5

Control TMP Acetoneextracted

TMP Ethylalcohol extracted

TMP Surfactantpretreated

ISO Brightness

Original


BiolubeCurrent Products

Markets for nonsulfurplant extractives


Related BioMass-BioFuels ActivitiesRagauskas Team

Lignocellulosicbiomass

Sugar/starchcrops

Oil plants>>Extractives<<

Gasification

Anaerobicdigestion

Flash pyrolysis

Hydrothermalliquefaction

Hydrolysis

Milling andhydrolysisPressing orextraction

Syngas

Biogas

Bio oil

Sugar

Plant Oil

Water gas shift+ separation

Catalyzedsynthesis

Purification

Hydro treatingand refining

Fermentation

Esterification

Hydrogen(H2)

Methanol(CH3OH)

DME(CH3OCH3)

FT Diesel(CxHy)

SNG(CH4)

Biodiesel(CxHy)

Ethanol(CH3CH2OH)

Biodiesel(alkyl esters)

Bio oil

Early Adoption/Paper Mill Sludge-Municipal Waste

OO

HOOH

OO

HOOH

OH

OH

O

HOOH

OO

HOOH

O-Cellulose

OH

OH

O

Ethanol from Cellulosic Waste

Glucose

Ethanol

Bark for Biofuels/Biochemicals`

Conversion Chemistry• Cat. Pyrolysis Chemistry

OH

OCH3

R

OH

OHOH

OHOH

OCH3

OH

Phenolics Feedstocks

Green Diesel/Gasoline

Bark for Biofuels/Biochemicals`

Pyrolysis of Black Liquor

Hydrogen Carbon Oxygen Sulfur Ash Sample name [wt%] [wt%] [wt%] [wt%] [wt%] Black Liquor 3.63 35.14 33.80 4.13 23.30 BL Solid 2.36 36.06 30.24 1.53 29.81 BL Pyr. Oil 8.88 67.69 17.18 2.19 4.06

UnaccountedUnaccounted(Gas)(Gas)

Solid yieldSolid yield(Char)(Char)

Pyrolysis oil Pyrolysis oil yieldyield

14.7814.7842.2542.2542.9842.98P 9.5 (extracted)P 9.5 (extracted)0.920.9267.5567.5531.5331.53P 9.5 (crude)P 9.5 (crude)2.712.7164.1464.1433.1633.16Black liquor (crude)Black liquor (crude)

[wt%][wt%][wt%][wt%][wt%][wt%]SampleSample

UnaccountedUnaccounted(Gas)(Gas)

Solid yieldSolid yield(Char)(Char)

Pyrolysis oil Pyrolysis oil yieldyield

14.7814.7842.2542.2542.9842.98P 9.5 (extracted)P 9.5 (extracted)0.920.9267.5567.5531.5331.53P 9.5 (crude)P 9.5 (crude)2.712.7164.1464.1433.1633.16Black liquor (crude)Black liquor (crude)

[wt%][wt%][wt%][wt%][wt%][wt%]SampleSample

Profiling Biomass Resources Kraft Lignin Isolation

Assorted Possibilities

Ultra-filtration

Low MW Lignin

High MW LigninEvaporators

To recovery boiler

Black liquor

Dewatering

Washed lignin

Precipitation vessel

Wash liquor

“Re-slurry” tank

Weak black liquor tank

Acid Precipitation

Profiling Biomass Resources Kraft Lignin Application: Carbon Fibers

10% of U.S. kraft lignin is sufficient to produce enough carbon fiber to replace half of the steel in all domestic passenger transport vehicles

153-172189-19895/5

120-157150-18275/25

138-172191-20087.5/12.5

138-165195-228100/0

Alcell (°C)HWKL (°C)Lignin/PEO

153-172189-19895/5

120-157150-18275/25

138-172191-20087.5/12.5

138-165195-228100/0

Alcell (°C)HWKL (°C)Lignin/PEO

Alcell and Hard Wood Kraft Lignin (HWKL) were spun continuously into satisfactory fibersAlcell/PEO blends: inter-fiber fusing SWKL: formed chars instead of fibers

Profiling Biomass Resources Kraft Lignin Application: Pellet Binder

District Heating

Drivers for Wood Pellets • Investment Tax Credit• Capital Grants• Consumer Rebates• Excise Tax Exemptions• Tax Credits• Targets/Quotas with Penalties• Subsidies

• Production of Green Electricity• Consumption

Lignin: Binder for Wood Pellets

Profiling Biomass Resources Kraft Lignin Application: Resin/Adhesive

Strength Properties of OSB-Panels Produced with Combination of Phenolic Resin and Lignin

Binder Property 100% Phenolic 80% Phenolic/20% Lignin Powder Resin MOR/psi 3456 3654 IB/psi 59.4 60.1 D-4/lbs 144 143 D-5/lbs 115 141 Liquid Resin MOR/psi 5204 4866 IB/psi 83 295 D-4/lbs 276 97

Novel Oxidative/Reductive Chemistryfor Lignin

OH

OH

OCH3HO

OCH3

O

HO

HO

H3COO

HO

HO OCH3

O

HOOCH3

OHO OH

OOH3CO

HO

HO

O

OH

OH

OCH3

OCH3

OH

OH

OOCH3

OO

OCH3

O

OCH3

HO

HO

OCH3

O

O

OCH3

HOO

HO

HO

OCH3

C8 – C22

OH

HO

O OCH3

O

OCH3

O

HO

O OCH3

O

OCH3

Oxid.

∼ C800 – C900

OH

HO

O OCH3

O

OCH3

OH

HO

HO OCH3

O

OCH3

H2/Cat

Catalytic Conversion of Biomass to Biofuels

Biofuel precursor:Biofuel precursor:

OH

OH

OCH3HO

OCH3

O

HO

HO

H3COO

HO

HO OCH3

O

HOOCH3

OHO OH

OOH3CO

HO

HO

O

OH

OH

OCH3

OCH3

OH

OH

OOCH3

OO

OCH3

O

OCH3

HO

HO

OCH3

O

O

OCH3

HOO

HO

HO

OCH3

CC99 –– CC1818

∼∼ CC800800 –– CC900900

Cracking BiopolymerCracking Biopolymer Viable BiodieselViable Biodieselor Biogasolineor BiogasolineComponentComponentCurrent Research Activities:Current Research Activities:

-- Utilization of conventional Utilization of conventional heterogeneous hydrogenationheterogeneous hydrogenationcatalystscatalysts

-- Development of homogenousDevelopment of homogenousaqueous phase catalysis aqueous phase catalysis chemistry for hydrogenationchemistry for hydrogenationcleavage of: cleavage of:

ArylAryl--OO--Aryl Aryl ArylAryl--OO--Aliphatic EthersAliphatic Ethers

BioChemical: Novel Reductive Catalytic Chemistry

BioMaterial PrecursorsOH

OH

OCH3HO

OCH3

O

HO

HO

H3COO

HO

HO OCH3

O

HOOCH3

OHO OH

OOH3CO

HO

HO

O

OH

OH

OCH3

OCH3

OH

OH

OOCH3

OO

OCH3

O

OCH3

HO

HO

OCH3

O

O

OCH3

HOO

HO

HO

OCH3

C6 – C24

∼ C800 – C900

Cracking Biopolymer

Current Research ActivitiesDevelop heterogeneous/homogenous aqueous

phase catalysis chemistryhydrogenation cleavage

Non-water-soluble hydrogenation complexes

Water-soluble hydrogenation complexes

Ruthenium [Ru(Cl)2( PPh3)3] [Ru(Cl)2( TPPTS)3] [Ru(H)(Cl)( PPh3)3] [Ru(H)(Cl)(TPPTS)3] [Ru(H)2(PPh3)4] [Ru(H)2(TPPTS)4] Rhodium [RhCl(PPh3)3] [RhCl(TPPTS)3]

Reductive

Experimental Setup

• 4560 Mini Parr reactor equipped with a 4842 temperature controller.

• Pressurized with UHP Hydrogen gas.

• Under on-line controlled time and pressure.

Lignin Hydrogenation

TgTg = 148 = 148 ±± 1 1 °°CC

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

Schlenk 50 C Parr 200 CParr

50 C 100 C 150 C 175 C 200 C

Reaction conditions

Mass Balance lignin Hydrogenolysis RuCl2(PPh3)3

CharredUnsolluble PhaseSolluble Phase

Lignin HydrogenationReaction conditions Solubility in

ethanol (% dry wt.)

Mn

(g mol-1) EOL * 52.1 1191 Blank * 65.0 1026 Heterogeneous catalysts Co/Mo 54.3 1075 Raney-Ni * 71.8 1148 Pd/C 69.8 995 Pt/C 76.5 953 Homogeneous catalysts NaBH4/I2 * 72.4 404 RhCl(PPh3)3 76.3 787 Ru(Cl)2( PPh3)3 * 96.4 893 Ru(H)(Cl)( PPh3)3 77.2 837 Ru-(PVP) 58.1 902

Profiling Biomass Resources Kraft Lignin Application

Phenols, Cresols Phenol, Acetic Acid Acetylene Substituted Phenols Substituted Phenols, CO, CH4 Ethylene HYDROGENATION PYROLYSIS FAST PYROLYSIS Phenol HYDROLYSIS ALKALI Phenolic Acids Substituted Phenols Catechols OXIDATION MICROBIAL OXOREDUCTASE Vanillin, MeS2 Lignin with Increased Vanillic, Ferulic Oxidized Lignin MeSH, DMSO Polymerization Coumaric/other Coating/Paint Acids Additive

Thank You!

W.J. BryanDestiny is not a matter of chance, it is a matter of choice, it

is not a thing to be waited for, it is a thing to be achieved

forest biorefineries transforming the forest products industry

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