All Biorefineries Are Regional Biodiesel Biogasoline BioFuels US: - - PowerPoint PPT Presentation

The challenges and Opportunities for Next Generation

• f Forest Product Biorefineries

Arthur J. Ragauskas School of Chemistry and Biochemistry Institute of Paper Science and Technology Georgia Institute of Technology

All Biorefineries Are Regional

Biodiesel Biogasoline

BioFuels

1000 2000 3000 4000 5000 6000 7000 1980 1982 1984 1986 1988 1990 1992 1994 1996 1998 2000 2002 2004 2012

U.S.A. Bioethanol MM Gal. Annual

US: Currently Bioethanol 2% Biodiesel 0.01%

O HO HO OH OH OH

Today

Amylase Yeast

H3C H2 C OH

O HO HO OH OH OH

Today

Amylase Yeast

H3C H2 C OH

O HO HO OH OH OH O HO HO OH OH

Future Biomass Acid Catalyst

• r

Enzymes

Fermentation

H3C H2 C OH

Others

LignoCellulosics Bioresource

Lignin Polymer Derived from Coniferyl, Coumaryl, Sinapyl, Alcohol Major Global Biopolymers Hemi Cellulose Short chain branched,substituted polymer of sugars DP: ~ 70 - 200 Cellulose Polymer of β-(1,4)-glucan DP: ~300 – 15,000

Content: ~ 35 – 50% Content: ~ 20 - 30% Content: ~ 15 – 30%

Lignin Polymer Derived from Coniferyl, Coumaryl, Sinapyl, Alcohol Major Global Biopolymers Hemi Cellulose Short chain branched,substituted polymer of sugars DP: ~ 70 - 200 Cellulose Polymer of β-(1,4)-glucan DP: ~300 – 15,000

Content: ~ 35 – 50% Content: ~ 20 - 30% Content: ~ 15 – 30%

BioResource % ∼ Lignin Hemicellulose Cellulose Softwood 27 28 39 Hardwood 25 30 40 Corn Stover 18 22 38 Wheat Straw 23 21 38 Fine Paper

• 20

80 Switch Grass 18 21 31

LignoCellulosic BioResources

DOE

Forest Biorefinery Today’s Industry Situation

• U.S. forest products industry is an important and vital segment
• f the nation’s economy

– Is the world’s largest manufacturer of forest products – Directly employs over 1.3 million people – Ranks among the top ten manufacturing employers in 42 states – Estimated payroll of $50 billion. – Sales top $230 billion annually in the U.S. and export markets.

• BUT…

– Industry has not earned its cost of capital in a decade – Mergers and Acquisitions

• Necessary for survival
• Won’t solve major problem

Forest Products – Return on Equity 1990 – 1995

Forest Biorefinery Today’s Industry Situation

World has Changed

– Tropical pulp mills have advantage in the HW market – China is filling their needs with modern, high-technology, low-cost mills – Competition from foreign- made products in the U.S. market is growing

• Two choices

– Allow production (and supply chains) to migrate offshore – Introduce new line of products to provide significant growth

Pulp and Paper Forum 2005 Techno-Business Innovation and Transfer

From Wood to Market Pulp

+ +

Wood

Cellulose Lignin Cellulose Hemicellulose

Cooking bleaching stages Bleached pulp

Today’s Forest Products BioRefiner

Lignin Cellulose Hemicellulose Lignin

Paper

• Carbohydrates

Products

Thermal Energy

• Lignin
• Carbohydrates

Kraft Pulping-Bleaching Greenfield Mill: $1 – 2 Billion Collects: 650,000 tons of wood/year Generates: 350,000 tons of pulp US: 110 million tons pulpwood/year

Pulping Wood: Chemically

Major Chemical Pulping Processes

• Chemical wood pulp fibers are

manufactured by chemically dissolving lignin from the wood liberating fibers.

• Maximize lignin removal
• Maximize carbohydrate retention
• Kraft Process - 1879 in Germany
• Harsh Conditions

Softwood and Hardwood Kraft Pulping Conditions. Softwood Hardwood Active alkali on dry wood 17 - 21 % 14 – 18 % Liquor sulfidity (Na2S) 25 % 25 %

• Max. cooking temperature/ oC

170 170 Total cooking time/min 112 - 174 63 – 95 Kraft cook completed at lignin content 5 % 2 % Yield 48 – 43 49 – 47

Today- Tomorrow’s Forest Products BioRefiner

Wood Debarking Collection Wood Chipping Pulp Bleaching Papermaking Energy Pulping Chemicals Bark Energy Unbleached Pulp Papermaking Wood Chips Pulping Combustion of Chemical Pulp Waste Proposed Hemicellulose Extraction Stage Extracted Woodchips Wood Hemicellulose Sugars Bioethanol Fermentation Wood Extractives Chemical Markets Biofuels Value-Added Chemicals

Current Products: Pulp, Tall Oil, Turpentine Future Select Hemicellulose

BioRefinery: Kraft Mill Opportunities

Typical Wood Chemical Distribution for Wood Before and After Kraft Pulping

Component Wood Components Kraft Pulp Components Pine Birch Pine Birch As a % of Original Wood Cellulose 38 – 40 40 – 41 35 35 Glucomannan 15 - 20 2 - 5 5 1 Xylan 7 - 10 25 – 30 5 16 Other carbohydrates 0 - 5 0 – 4

• Lignin

25 - 30 20 – 22 2 – 5 1.5 – 3 Extraneous compounds 4 - 6 2 - 4 0.25 < 0.5

Typical kraft pulp mill will utilize ∼630,000 tons of wood/year Approximately 90,000 tons of hemicellulose/year are degraded

BioRefinery: Hemicellulose Extraction

Research Background: Kraft pulping selectively degrades hemicelluloses

. Carbohydrate Profile for Loblolly Pine Wood and Kraft Pulp. Source Glucose Galactose Mannose Xylanose Arabinose Wood 67.9 3.5 17.7 8.8 2.1 Pulp 84.9 0.3 7.1 7.1 0.5

Mayor Chemical Constituents of Wood. Wood Macromoleculesa Wood Species Cellulose (%) Lignin (%) Hemicelluloses (%) Softwoods Picea glauca 41 27 31 Abies balsamea 42 29 27 Pinus strobes 41 29 27 Tsuga Canadensis 41 33 23 Thuja occidentalis 41 31 26 Hardwoods Acer rubrum 45 24 29 Ulmus Americana 51 24 23 Populus tremuloides 48 21 27 Betula papyrifera 42 19 38 Fagus grandifolia 45 22 29

aall samples were analyzed extractives free

Potential Process Benefits from Pre-Extracting Hemicelluloses Prior to Kraft Pulping

• Increased pulp production for recovery furnace limited pulp operations
• Improved pulp properties due to enhanced cooking liquor impregnation in the wood chips
• Improved kraft cooking conditions requiring reduced cooking chemicals

BioRefinery: Pre-Extraction Considerations

Cellulose DP: ∼ 1600 post-pulping, ∼ 700 post-bleaching Hemicellulose: α-cellulose content > ∼80%, a decrease paper sheet strength properties occurs.

BioRefinery: Hemicellulose Extraction

Overview of Experimental Plan

Southern Loblolly Pine Chips Control Kraft Pulping Wood Chips Kraft Pulping Pulp Yield Fiber Properties Paper Properties Hemi-Extracts Pulp Yield Fiber Properties Sheet Properties Hemi Yield Lignin Yield Hemi Composition

Wood Chip Pre-extraction Acidic – Basic

BioRefinery: Hemicellulose Extraction

Experimental Pre-Extraction Conditions

Loblolly 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

O O O OAcO O HO OAc O HO O O O AcO OH O-Xylan O O HO OAcO O AcO OAc O O HO HO O HO O OH HO OH O HO HO OH O O O OH O O HO OH O HO O O O HO OH O-Xylan O O HO OAcO O HO OH O O HO HO O HO O OH HO OH O HO HO OH

+ HOAc

BioRefinery: Hemicellulose Extraction

Kraft Pulping Steam Pretreated Woodchips: Approach

Steam < 3% Yield

Acidic Pre-Extractions – Kraft Pulping

BioRefinery: Hemicellulose Extraction

Acidic Pre-Extracted Woodchips: Monosaccharide Analysis

Mass Terminal pH % Recovery

0.5h Pre-Extraction 0.0% H2SO4: 5 3.2 0.2% H2SO4: 5 2.7 0.5% H2SO4: 8 2.3 1.0h Pre-Extraction 0.0% H2SO4: 8 3.7 0.2% H2SO4: 10 2.4 0.5% H2SO4: 12 2.2

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

Yields 10 – 18%

BioRefinery: Hemicellulose Extraction

5 10 15 20 25 30

Kappa #

C

• n

t r

• l

( n

• p

r e

• e

x t r a c t i

• n

) . 5 h r p r e

• e

x t r a c t e d / W i t h w a s h i n g . % H 2 S O 4 . 2 % H 2 S O 4 . 5 % H 2 S O 4 1 . h r p r e

• e

x t r a c t e d / W i t h w a s h i n g . % H 2 S O 4 . 2 % H 2 S O 4 . 5 % H 2 S O 4 1 . h r p r e

• e

x t r a c t e d / W i t h

• u

t w a s h i n g . % H 2 S O 4 . 2 % H 2 S O 4 . 5 % H 2 S O 4

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

BioRefinery: Hemicellulose Extraction

Kraft Pulping Acidic Pre-Extracted Woodchips: Viscosity

0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0

Viscosity/cP

Control(no pre-extraction) 0.5hr pre-extracted/With washing 0.0 % H2SO4 0.2% H2SO4 0.5% H2SO4 1.0hr pre-extracted/With washing 0.0 % H2SO4 0.2% H2SO4 0.5% H2SO4 1.0hr pre-extracted/Without washing 0.0 % H2SO4 0.2% H2SO4 0.5% H2SO4

BioRefinery: Hemicellulose Extraction

Kraft Pulping Acid Pre-Extracted Woodchips: Burst Index

0.0 0.5 1.0 1.5 2.0 2.5 Original 0.5hr pre-extracted(with washing) 0 % H2SO4 0.2% H2SO4 0.5% H2SO4 1.0hr pre-extracted(with washing) 0 % H2SO4 0.2% H2SO4 0.5% H2SO4 1.0hr pre-extracted(without washing) 0 % H2SO4 0.2% H2SO4 0.5% H2SO4 Burst Index

Burst Index

BioRefinery: Hemicellulose Extraction

Acidic Pre-Extracted Woodchips: Pretreatment Modification Prior Studies Direct

H2SO4/H2O t=0 H2SO4/H2O t= 48 h Spray Chips 1 h, 150 oC

Alternative Approach Delayed

BioRefinery: Hemicellulose Extraction

Acidic Pre-Extracted Woodchips: Pretreatment Modification

H2SO4/H2O Direct & Delayed 1 h, 150 oC Reducing Sugars (mg/ml) % Hemicellulose 0.5% H2SO4 Direct (t:0) 36.3 12 Delayed (t: 48 h) 57.8 19 0.75% H2SO4 Direct (t:0) 67.9 22 Delayed (t: 48 h) 72.2 23

Basic Pre-Extractions – Kraft Pulping

BioRefinery: Hemicellulose Extraction

Acidic Pre-Extracted Woodchips: Pretreatment Modification

NaOH/H2O 1 h, 150 oC Exp. Terminal pH %Sugar Recovery Reducing Sugar (mg/ml) 150 oC 4.5% NaOH 1.0 h: 10.6 8 1.9 160 oC 4.5%% NaOH 1.0 h: 10.0 11 2.0 170 oC 4.5% NaOH, 2 h 8.9 11 2.3 6.0% NaOH, 1 h 11.3 14 2.5 9.0% NaOH, 1 h 12.7 16 3.3 12.0% NaOH, 1h 12.7 18 4.0

BioRefinery: Hemicellulose Extraction

Kraft Pulping Alkali Pre-Extracted Woodchips: Kappa #

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

10 20 30 40 50 60

% Monosaccharide 150 C NaOH 4.5%, 1hr 160 C NaOH 4.5%, 1hr 170 C NaOH 4.5%, 1hr NaOH 4.5%, 2hr NaOH 4.5%, 3hr NaOH 6.0%, 1hr NaOH 9.0%, 1hr NaOH 12.0%, 1hr

Arabinose Galactose Glucose Xylose Mannose

Exp. Terminal pH 150 oC 4.5% NaOH 1.0 h: 10.6 160 oC 4.5%% NaOH 1.0 h: 10.0 170 oC 4.5% NaOH, 1 h 9.1 4.5% NaOH, 2 h 8.9 4.5% NaOH, 3 h 8.0 6.0% NaOH, 1 h 11.3 9.0% NaOH, 1 h 12.7 12.0% NaOH, 1h 12.7

Post-Pulping Approach

• Extraction of cellulose- and lignin-derived chemicals from

black liquor

• Recovery of tall oil soap and extractives from black liquor
• Gasification of black liquor residuals, wood waste, and
• ther biomass to produce syngas
• Conversion of syngas to methanol, DME, ethanol, Fischer

Tropsch fuels, etc.

Production Costs from Biomass-Derived Syngas Competitive in Some Cases

Spath and Dayton, 2003

Opportunity: The Forest Biorefinery

• The Chemical Pulp Mill has

– Existing infrastructure to procure, receive, store, and handle harvested wood – Skilled labor force – The permits needed to operate – Capital Infrastructure

• Program needs consists of three parts:
• 1. Sustainable Forest Productivity
• 2. Extracting Value Prior to Pulping
• 3. New Value Streams from Residuals and Spent Pulping Liquors

Syngas Syngas Power Export $3.8 billion

• r

Liquid Fuels/Chemicals $5.5. billion

O2

Pulp $5.5 billion Steam, Power & Chemicals

BL Gasifier Wood Residual Gasifier Combined Cycle System Process to manufacture Liquid Fuels and Chemicals

The Forest Biorefinery – Net Revenue

Manufacturing

CO2

Extract Hemicelluloses new products chemicals & polymers $3.3 billion

Black Liquor & Residuals

Net Revenue Assumptions:

Acetic Acid - $1.73/gallon Purchased Electricity - $43.16/MWH Ethanol - $1.15/gallon Exported Electricity - $40.44/MWH Pulp - $100/ton net profit Renewable Fischer Tropsch Fuel - $57/bbl

BioRefinery: Kraft Mill Opportunities

Select Hemicelluloses

Projected Net New Ethanol Revenue: $4 – 5 MM/mill

Future Forest Biorefinery Goal

• Evolve existing pulp mills into forest biorefineries that

– Produce fuels, chemicals, and power streams – Continue to meet growing demands for traditional pulp and paper products – Increase revenue while protecting core business

• Excellent alignment with the mandates of government

agencies striving to improve the nations’ energy self- sufficiency

• Valued by society and the marketplace because they help

preserve infrastructure, jobs, supply chains & permits

Syngas Syngas Power Export 116 million BOE

• r

Liquid Fuels/Chemicals 109 million barrels

O2

Pulp SW 55 million tons

Steam, Power & Chemicals

BL Gasifier Wood Residual Gasifier Combined Cycle System Process to manufacture Liquid Fuels and Chemicals

Manufacturing

CO2

Extract Hemicelluloses new products chemicals & polymers 1.9 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

Synergies between TC Processes and the Sugars Biorefinery

Lignocellulosic Biomass

Fermentation

Catalysis Syngas Production Sugar Production Ethanol

Products: propanol, butanol

• ther alcohols

Products: polyols, organic acids,

• thers

Lignin-rich Residues Low Quality Residues CHP Distillation

• H

• H2O

• H2O

Pulping Wood: Chemically

Kraft Pulping: Tall oil production

– C18 tall oil fatty acids, terpenes (Turpentine) 825,000 Total 100,000 MeadWestvaco, De Ridder, La. 115,000 MeadWestvaco, Charleston SC 75,000 Eastman Chemical, Savannah, Ga. 75,000 Eastman Chemical, Franklin, Va. 20,000 Hercules, Burlington, Ontario 130,000 Georgia-Pacific, Crossett, Ark. 120,000 Arizona Chemical, Savannah, Ga. 110,000 Arizona Chemical, Port St Joe, Fla. 80,000 Arizona Chemical, Panama City, Fla. CAPACITY

(short tons)

PRODUCER

HO H

Pine Sitostanol

CO2H H H

Abietic Acid

Oleic Acid:CH3(CH2)7CH=CH(CH2)7COOH

Food Additive

Todays Forest Biorefinery

O2 Pulp CO2

Steam, Power & Chemicals

BL Recovery Boiler Power Boiler Black Liquor & Residuals

Current Mill

Manufacturing Purchased Power – 6 GW $2.0 billion

CO2

Summary of Syngas-Liquids Processes

Syngas CO + H2 Methanol

H2O WGS Purify

H2

N2 over Fe/FeO (K2O, Al2O3, CaO)

NH3

Cu/ZnO

Isosynthesis ThO2 or ZrO2

i-C4

A l k a l i

• d
• p

e d Z n O / C r2 O3 C u / Z n O ; C u / Z n O / A l2 O3 C u O / C

• O

/ A l2 O3 M

• S2

Mixed Alcohols

Oxosynthesis

H C

• (

C O )4 H C

• (

C O )3 P ( B u3 ) R h ( C O ) ( P P h3 )3

Aldehydes Alcohols

Fischer-Tropsch

Fe, Co, Ru Waxes Diesel Olefins Gasoline

Ethanol

Co, Rh Formaldehyde A g DME

Al2O3

zeolites MTO MTG Olefins Gasoline

MTBE Acetic Acid

carbonylation CH3OH + CO Co, Rh, Ni

M100 M85 DMFC Direct Use

h

• m
• l
• g

a t i

• n

C

• isobutylene

acidic ion exchange

Source: R. Bain, NREL, 2004

The Forest Biorefinery Research Needs

• Develop technology to effectively

– Extract hemicelluloses from wood chips – Economically convert extracted hemicelluloses into biofuels and biochemicals – Remove remaining barriers to gasification of spent pulping liquors – Economically convert syngas into fuels and chemicals – Effectively integrate the new processes into existing mill infrastructure

• Develop sound economic studies
• Partner with government agencies/companies whose mandates

are aligned with our goal

The Forest Biorefinery

The Forest Products Industry and Partners have a unique opportunity:

• Tap the enormous potential of managed forests for

Paper, Biofuels, Electricity, and Biomaterials

• Reduced green house gases and benefit environment
• Manufacture sustainable products and energy
• Leverage Existing Forest Products Resources to

Reinvent Itself

?When?

Acknowledgements IPST@GT Member Companies USDA, NSF

arthur.ragauskas@ipst.edu or http://home.ipst.edu/~aragausk//