October, 2006 ESPRI / PBE

Energy OutlookLife Goes On After Fossil Depletion

Shijie LiuFaculty of Paper and Bioprocess Engineering& Empire State Paper Research Institute

SUNY ESF1 Forestry Drive, Syracuse, New York

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Outline Energy Resources Biomass Based Energy & Chemicals Paper Industry

– Near-term Application: Hot-water Extraction– Wood Extract Use– Alkaline Pulping & Fiber Quality– Black Liquor Gasification

Conclusion Life Goes on After Fossil Depletion

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Energy Resources Sun

– Hydro, plants Hydro and Geothermal Energy

– Location– Environmental / ecological

Plants– Biomass– Animals

Coal, Petroleum Nuclear Energy

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Energy Consumption: Quadrillion Btu / year

Year Renewables Nonrewables

1990

2000

2010

2020

26.440

32.333

39.788

45.194

321.775

366.913

463.656

552.603

1990

2000

2010

2020

6.132

6.158

7.081

8.003

78.564

92.827100.711

112.582U.S

.A.

Wor

ld

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US Pulp and Paper Industry

Main raw material: forest wood

Accounts for 6.9% Coal, Oil, Gas and Electricity of all manufacturing industries

1.3% total US fossil energy consumption 1.1% of all US energy 0.27% of the world energy diet

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Energy Resources

Chemical Recycle Time

Algae

Agricultural Crops

Grasses

Shrubs

Trees

Oil, Gas and Coal

1 Month

3 Months ~ 1 Year

1 Year

1 ~ 5 Years

5 ~ 80 Years

200 million Years

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Energy Resources Availability

– Quality– Technology

Reliability– Proximity– Stability

Affordability– Economical– Environmental– Societal

Equivalence in energy

wood to petroleum:

$100 / ton $34 / Barrel

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Environmental Impact

USA Government: displacing 10% of the petroleum with biomass derived fuel and products by 2020. (DOE Vision for Bioenergy and Biobased Products in the United States, October 2002).

Greenhouse gases (GHG) are increasing: in 2000, the atmosphere held about 774 Pg (774 billion metric tonnes) of carbon as CO2, 369 vppm (Marland & Boden, 2001). The total will double by the end of this century if not controled. To stabilize CO2 at about 550 vppm, it is necessary to reduce net GHG emissions. USA alone is expected to release 1.8 Pg of carbon in 2010 and 2.1 Pg of carbon in 2020, about 25% of the world total (EIA 2000). Most of current carbon emission is a direct result of the use of fossil fuels.

SEEK NEW SUBSTITUTED FUEL derived from biomass

Ethanol, butanol, acetone

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energy

O2

CO2, H2O

(CH2O)n O2

Why Biomass?

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Pulp and Paper Industry

Unique PositionRaw materials

Material handling capacity

Experience Question to answer:

Can wood be harvested and chipped when fossil energy had been exhausted?

Paper Industry

Plant Biomass

Volatile Extractives Lignin Hemicelluloses Cellulose

Chemicals Energy Sugars

Biodegradable Plastics

Paper

Ethanol ButanolBio-Diesel

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Wood Composition Inorganic Components

K & Ca (400 ~ 1000 ppm);

Mg & P (100 ~ 400 ppm) ; and 70 others Extractives

Aliphatic and alicyclic: Terpenes; terpenoids; esters; fatty acids; alcohols; …

Phenolic: phenols; stilbenes; lignans; isoflavones; …

Others: sugars; cyclitols; tropolones; amino acids, … Hemicelluloses Celluloses

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(phenols)

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Hemicelluloses Hardwood:

– Glucomannan – Glucuronoxylan (Xylan)

Softwood:– Galactoglucomannan– Arabinoglucuronoxylan (Xylan)

Xylan: Polymer of 5-Carbon Sugar

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Near-term Applications

Biorefinery Extraction prior to Pulping Fractionation of Wood Extracts Fermentation

Black Liquor Gasification

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Wood harvesting

DebarkingWood chipping

Wood chips

Pulping

Extraction

Hemicellulose

Bioethanol

Bleaching

Papermaking

Degraded Lignin and carbohydrates

Bark Value-added chemicals

Energy

Energy

Butanol

Lactic acid

Biodegradable polymer

Near-term Application

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Hot-Water Extraction

Abundant Safety, Environmental, Reuse Catalyst Use Product Value Product Separation

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Hot-Water Extraction

Aspen WoodGlucan: 44.5%

Xylan: 17.7%

Galactan: 1.3%

Arabinan: 0.5%

Mannan: 1.7%

Klason Lignin: 21.1%

Others: 13.2%

Residual Wood: 81.8%

44.7% Glucan

8.8% Xylan

0.0% Galactan

0.0% Arabinan

1.2% Manan

20.9% Klason Lignin

6.2% OthersWood Extracts:

18.2%

0.7% Glucan

9.1% Xylan

0.8% Galactan

0.4% Arabinan

0.6% Manan

1.1% Klason Lignin

5.5% Others

Autocatalytic

Extraction

150C, 4.5h

Data from: U. Tschirner, et al. (2006)

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Fractionation Acetic Acid Acetates Hexoses, Pentoses Oligomers Methanol Aromatics Furfurals Catalyst

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Ethanol Production

Anaerobic Fermentation: Sugar is SugarC6H12O6 2 C2H5OH + 2 CO2

3C5H10O5 5 C2H5OH + 5 CO2

Theoretical yield: 51.14% (lb-ethanol/lb-sugar)

“Poly-glucose”: (Cellulose, glucomannan, …)HO(C6H10O5)nH + (n–1)H2O 2nC2H5OH + 2nCO2

Contribution of water adds to 56.82%

“Poly-xylose”: (Xylan)3HO(C5H8O4)nH + 3(n–1)H2O 5nC2H5OH + 5nCO2

Contribution of water adds to 58.12%

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Effect of Hot-Water Extraction Hemicelluloses removal

– Uronic acid– Acetyl groups– Carboxyl groups– Metal ions

Lignin– Lignin-hemicellulose bonds– Active chemical agent access to lignin sites

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Alkaline Pulping & Fiber Quality Mild cooking / bleaching conditions Sulfur-free if desired

– Environmental– Black Liquor Gasification

TCF ? Low Hemicelluloses content

– High Freeness for the same other indices– High SEC to reduce freeness

Fiber-Fiber bonding Bulk

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Advantages

Bottom Line improvement Environmental benign modification to

existing processes enabling– Sulfur use on the way out– Chlorine, Chlorine Dioxide, on the way out– Value-added chemical and energy

byproducts Kraft Process?

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Conclusions Biorefinery: a strategic direction to

Energy and Chemicals ESF Biorefinery: water-based

technology Pulp and Paper Industry Adaptation:

Extraction; Fractionation; Fermentation; Pulping; Bleaching; Papermaking; Black Liquor Gasification

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Conclusions

Future depends on renewable energy and chemicals

Pulp and Paper Industry potential to play as a leader

Life will go on when fossil energy is depleted

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Life After Fossil Depletion

AutomobilesButanol; Propanol; Ethanol; Hydrogen

AirplaneButanol; Propanol; Hydrogen

Tractors, Combines, …Butanol; Ethanol; Bio-diesel

Cooking, Heating and LightingGreen power; Bio-gas; Bio-diesel; Bio-oil

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Acknowledgements T.E. Amidon G.M. Scott R.C. Francis B.V. Ramarao Y.Z. Lai

ESPRISPPFPBE StaffESF

Colleagues, Students, and Research Fellows

ESPRI / PBE

Thank You!