Creating a Bio-refinery Based Creating a Bio-refinery Based on Pulping Technologyon Pulping TechnologyDon Guay – Don Guay – Dept. of Paper Science & EngineeringDept. of Paper Science & Engineering

Eric Singsaas Eric Singsaas – Dept of Biology– Dept of Biology

UW – Stevens PointUW – Stevens Point

Biofuel barriers

•Feedstock

•Grains are not a long-term solution

•Cellulosic feedstocks must come from many sources

•Cellulose processing

•Low cellulose hydrolysis yield

•Cellulase enzymes are costly

•Requires caustic and energy-intensive pretreatment

•Many steps required for bioprocessing

•Products (ethanol)

•Low energy density compared with petroleum fuels

•Corrosive

•Transport issues

•Market saturation

Lee R Lynd, Mark S Laser, David Bransby, Bruce E Dale, Brian Davison, Richard Hamilton, Michael Himmel, Martin Keller, James D McMillan, John Sheehan & Charles E Wyman Nature Biotechnology 26, 169 - 172 (2008)doi:10.1038/nbt0208-169

AvailabilityAvailability

Existing forest harvestExisting forest harvest 142 million tons142 million tons

Residues and Residues and non-marketable biomassnon-marketable biomass 226 million tons226 million tons

Incompletely pulped materialIncompletely pulped material 1-10 tons/day per mill1-10 tons/day per mill

MiscanthusMiscanthus potential yield potential yield 10-15 tons/acre (UIUC)10-15 tons/acre (UIUC)6-10 tons/acre (ORNL)6-10 tons/acre (ORNL)

Unrecyclable paperUnrecyclable paper

Softwood pulpSoftwood pulp

Hardwood pulpHardwood pulp

Corn stoverCorn stover

MiscanthusMiscanthus grass grass

http://www.energy.iastate.edu/becon/tour/tourimages/02-corn_stover.jpg

SSFSSF

Size Size reductionreduction

Remove Remove HemicellulosHemicellulos

ee

Remove Remove LigninLignin CatalystCatalyst FermentationFermentationEnzymatic Enzymatic

HydrolysisHydrolysis

Treated softwood pulp

Untreated softwood pulp

Direct Bioproduction of Energy-Rich Direct Bioproduction of Energy-Rich Fuels Fuels This breakthrough, high-payoff opportunity focuses on microbes for direct production of hydrophobic alternative fuels (i.e., alkanes, longer-chain alcohols, and fatty acids). This would overcome one limitation of nearly all bioconversions—they result in dilute aqueous mixtures. Typical industrial product concentrations are 100 to 150 g/L for ethanol and other such products as organic acids. This limitation imposes separation requirements that increase process and energy costs. New fermentation systems would be highly desirable to allow significant increases in product concentration, new types of products, and new processes for product recovery. Strong increases in efficiency also could be achieved by developing continuous processes.

U.S. DOE. 2006. Breaking the Biological Barriers to Cellulosic Ethanol: A Joint Research Agenda, DOE/SC/EE-0095, U.S. Department of Energy Office of Science and Office of Energy Efficiency

and Renewable Energy, http://doegenomestolife.org/biofuels/.. Adapted from M. Himmel and J. Sheehan, National Renewable Energy Laboratory

EthanolEthanol Methyl- butenolMethyl- butenol IsopreneIsoprene

FormulaFormula CC22HH66OO CC55HH1010OO CC55HH88

Water solubilityWater solubilitymol mmol m-3-3 ∞∞ 11701170 11.711.7

Henry’s law coeff.Henry’s law coeff.Pa mPa m33 mol mol-1-1 0.5070.507 1.561.56 77807780

KKO/WO/W

mol molmol mol-1-1 0.490.49 17.817.8 263263

Energy contentEnergy contentBTU galBTU gal-1-1 85,00085,000 106,000106,000 135,000135,000

TTboil boil (°C / °F)(°C / °F) 78.4 / 17378.4 / 173 98.6 / 20998.6 / 209 33.9 / 92.933.9 / 92.9

Potential UsesPotential Uses FuelFuel FuelFuel Rubber productsRubber productsPharmaceuticalsPharmaceuticals

*BTU/gal. Gasoline energy content ranges 111,000-125,000

Tomohisa KUZUYAMA, “Mevalonate and Nonmevalonate Pathways for the Biosynthesis of Isoprene Units”, Biosci.

Biotechnol. Biochem., Vol. 66, 1619-1627 (2002) .

Glucose

Methyl butenol

IsopreneispS

MBO synthase

The MEP pathway

2-C-methyl-D-erythritol 4-phosphate

StructureStructure ClassClass ExampleExample UsesUses

C5C5 HemiterpeneHemiterpene IsopreneIsoprene Industrial ?Industrial ?

C5+OC5+O HemiterpenoidHemiterpenoid Methyl butenolMethyl butenol Biofuel ?Biofuel ?

C10C10 MonoterpeneMonoterpene ß-pineneß-pinene

C10+OC10+O MonoterpenoidMonoterpenoid Pyrethrin -IPyrethrin -I PesticidePesticide

C15 (+O)C15 (+O) SesquiterpeneSesquiterpene GossypolGossypol Male contraceptiveMale contraceptive

Modified sesquiterpenoidModified sesquiterpenoid ArtemisininArtemisinin Anti-malarial drugAnti-malarial drug

C20 (+O)C20 (+O) Diterpenoids (modified)Diterpenoids (modified) TaxolTaxol Anti-cancerAnti-cancer

C30 (+O)C30 (+O) TriterpenoidsTriterpenoids PhytosterolsPhytosterols Nutrient/medicalNutrient/medical

C40C40 TetraterpenoidsTetraterpenoids ß-caroteneß-caroteneLycopeneLycopene NutrientNutrient

Isoprenoids & their potential uses

Enabling technologies

•Metabolic control analysis of the MEP pathway

•Synthetic MEP pathway operon

•MBO synthase gene

•Bioreactor experiments

InputsInputsWaste paper and Mill sludgeWaste paper and Mill sludge

Papermill pulpPapermill pulp

Energy cropsEnergy crops

Forest productsForest products

StoverStover

ProductsProductsMethyl butenolMethyl butenol

IsopreneIsoprene

EthanolEthanolOther products?Other products?

http://www.ornl.gov/sci/besd/highlights.shtmlAccessed 11-15-07

Pulp Mills in Our regionPulp Mills in Our region

Research in progress – Benchtop

•Pulping

•Optimize catalyst and enzyme dosage

•Analyze product streams

•Develop microorganisms

•Consolidate bioprocessing

•Economic analysis

Cellulose Sciences, Inc.

Others

Our sincerest thanks to: