Helsinki University of Technology

Innovative Forest Products Biorefinery

Adriaan van Heiningen and Tapani Vuorinen

Helsinki University of TechnologyDepartment of Forest Products Technology

Espoo, Finland

III LiekkipaivaEspoo, January 31, 2007

Outline

• Future of the forest products industry• Biorefinery approach• Conversion strategy for hemicelluloses• Value-added/ODMT wood in biorefineries• Projects at HUT• Conclusions

Inflation Corrected Price of Northern Bleached Softwood Kraft Pulp

Pulp/Paper Capital Spending in N.A.

Facilities are not maintained below 75% expenditures(Kinstrey,R, Pulp and Paper. January 2004)

Pulp and Paper Industry Challenge • Due to global competition, pulp and paper prices

will continue to decrease. • Wood/biomass cost is correlated with energy

cost, so feed stock price is increasing• Profitability is “squeezed” from both sides

Traditional forest products industry needs more revenue from higher value-added products besides wood, pulp and paper products

How to Increase Revenue?

• Maximize pulp production• Make ethanol, chemicals and polymers

from hemicellulose• Make transportation fuel from lignin• Use bark and biomass as fuel for pulp mill

→Forest Biorefinery which produces pulp,paper and chemicals, fuels and polymers

Ultimate Biorefinery for Ligno-Cellulosics

• Goal: Clean fractionation in cellulose, lignin and hemicellulose, followed by further processing of these components into chemicals and materials

• Solvent choice: biomass contains water; water removal efficiency of multiple effect evaporation much more efficient than solvent distillation; use aqueous system as solvent

• Proven and versatile fractionation process for all ligno-cellulosics is kraft pulping. It yields fairly undegraded cellulose; however large fraction of hemicellulose is extensively degraded

Approach for Hemicelluloses

Hemicelluloses: - have low fuel value- are valuable in pulp- degrade during pulping- undegraded sugars needed for biofuels and chemicals

→Extract hemicelluloses before pulping

How to Obtain UndegradedHemicelluloses?

• Extraction of hemis as polymers before pulping

• Extract with water and chemicals which are compatible with the kraft process

• Minimize the amount of additional water introduced in the pulping process

• Hardwood and softwood need different approaches because their hemicelluloses are chemically different

Pulping Benefits of Hemicellulose Extraction

– Decreased alkali consumption– Reduced organic + inorganic load to

recovery– Increased delignification rate– Increased pulp production rate

Value of Cellulose Pulp Fibers

• Maximum theoretical yield of ethanol from cellulose pulp on weight basis is ∼ 50%

• Ethanol price must be at least > $1000/MT ($3.00/gallon) for economical conversion of cellulose ($500/MT) into ethanol

• Cellulose has high crystallinity, is durable and has unique structural properties

Pulp is more valuable than ethanol. Keeppulp as product in paper or structural products

Fuel Costs in Forest BiorefineryFuel Heating Value

(GJ/MT)Fuel Cost

(US$/Dry MT)Energy Cost

(US$/GJ)

Oil 43.5 555(US$60/barrel)

11.8

Biomass(20% moisture)

15 55 3.7

Black Liquor (20% moisture)

12.6 75 x 3/4 = 56(org/inorg = 3/1)

4.4

Lignin 26.9 75 2.8Carbohydrates 13.6 75 5.5

•Do not use oil!•Obtain energy from biomass and/or black liquor!•Minimize use of carbohydrates for energy purposes

Wood Extraction

Biomass(bark, etc.)

Solid Wood

Wood Fiber

Raw WoodExtract

Alkaline Pulping

OxygenDelignification

Pulp Bleaching

BleachedPulp

BlackLiquor

Black Liquorgasification

ElectricPower

HighPressureSteam

White Liquor(NaOH +

AQ)

Wood Modification

Wood ExtractConversion

Sugar-based

Polymers

WoodExtractFiltrate

CarbonFibers

WoodComposite

Biomass Gasifier Power +Steam

NaOH

Trees

SynthesisGas Diesel Fuel

Ethanol

IFPRIFPR

Existing Products

Existing Processes

New Processes

=

=

=

Legend

= Νεω Προδυχτσ

Hemicellulose Conversion Strategy

• Produce oxygen containing products to increase yield, shorten conversion path and competitiveness relative to petroleum-based

• Thus, produce alcohols, carboxylic acids, lactones, and esters

• Bio and catalytic conversions must work for both C5 and C6 sugars

Maximizing ValueProduct Price ($/ODMT) Yield (%) Value (US$/ODMT wood)Pulp 500 45 225Wood as fuel 55 55 30Total 100 255

Present situation

Value-Added: 255 – 75 = 180 US$/ODMT wood

Future SituationProduct Price Wood Yield (%) Conversion (%) Value (US$/ODMT wood)

Pulp $500/ODMT 45 100 225Polymer $3000/MT 10 50 150PU foam $3000/MT 10 45 135Diesel $630/MT

$2.00/gallon35 40 88

Total 100 598

Value-Added: 598 – 75 = 523 US$/ODMT wood

Development Challenges

• Maintain yield an quality of pulp• Selective and economic pre-extraction of

hemicellulose polymers• Efficient and high yield conversion of extract into

ethanol, chemicals and polymers.• Efficient and economic purification processes • Integration with beneficial effects on pulp

production• Demonstrate pressurized kraft black liquor

gasification at the mill scale

Projects at HUT

• Extraction Kinetics of Hemicelluloses

• High Temperature Degradation Kinetics of Black Liquor in the Liquid Phase

Extraction Kinetics of Hemicelluloses

• Variables: T, t, pH, ultrasound• Wood type: birch and pine• pH control: CO2/HCO3

-/CO32- buffers

• Equipment: “Berty” type CSTR• Analysis: - on-line UV and RI

- off-line TOC, TIC, TN, MeOH, HAc, sugars

- extracted wood composition- reducing ends in extracted wood

Berty CSTR

Liquor tankO2Gas

Controller

280 ml Reactorwith a 100 ml basket

Heat Exchanger

Heating

Flow IndicatorUV

spectro.

ComputerDomain Controller

Needle Valve

BFP

Cold Water

CO2

Berty Stationary Basket Reactor

• 2-inch inside diameter and 2-inch height basket

• Maximum 5800 psig, 343ºC

• basket volume is 100 ml and the free volume is 280 ml

Autoclaveengineers Co.

Setup at UMaine

Collaborations?

• Antti Grönroos, VTT Jyvaskyla• Pertti Koukkari, VTT Espoo• Liisa Viikari, University of Helsinki• Kari Saviharju, Andritz Oy• Others?

Degradation Kinetics of Black Liquor in Liquid Phase

• Variables: T, t, pH• Black liquor: Pine kraft• Equipment: Multiple small batch reactors• Analysis: - Pressure

- Gas composition incl. TRS + NOx- Liquor composition + properties

Collaborations?

• Pat McKeough, VTT Jyvaskyla• Raimo Alen, University of Jyvaskyla• Carl-Johan Fogelholm, HUT• Miko Hupa, Abo Akademi• Kari Saviharju, Andritz Oy• Others?

Conclusions

• Protects the Core: Increases the profits in support of traditional forest products production

• Ecofriendly: Transportation fuels, power, and bioproducts from a carbon-neutral, renewable resource

• Low Capital: Use existing pulping equipment and infrastructure for production of new, high value-added products besides traditional wood and paper products

• Synergy: Full integration of the traditional forest products and new bioproducts will lead to synergies

• Self-Sufficiency: Replacement of imported fossil fuels by domestic renewable fuel

• Employment: Preserves and creates jobs in rural forest-based communities

Benefits of Forest Biorefinery:

Coproducts Pulp + Transportation FluidsPulp ProductionProduct Price ($/ODMT) Yield (%) Value (US$/ODMT wood)Pulp 500 45 225Wood fuel 55 55 30Total 100 255

Value-Added: 255 – 75 = 180 US$/ODMT wood

Product Price Wood Yield (%) Conversion (%) Value(US$/ODMTwood)Pulp $500/ODMT 45 100 225

Ethanol from hemi

$670/ODMT$2.00/gallon

10 43 29

Diesel $630/ODMT$2.00/gallon

45 40 113

Total 100 367

Pulp and Transportation Fluids Coproduction

Value-Added: 367 – 75 = 292 US$/ODMT wood

What Products?(Mike Pacheco, NREL)

Examples of Potential Hemicellulose-Derived Chemicals• Ethyl levulinate, a diesel additive. Made from

esterification of levulinic acid with ethanol• 1,3 propane diol, the monomer for Dupont

polyester Sonomo® made from this diol and phtalic anhydride. Diol is made from HPA.

• Poly-itaconic acid. Made from sugar monomers by fermentation and then polymerization.

• Engineered wood products. Use of the new unsaturated polymers in wood composites (for example polypropylene fumarate?)

• 1,2 propylene glycol. Non toxic anti freeze