innovative forest products biorefinery -...
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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
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Outline
• Future of the forest products industry• Biorefinery approach• Conversion strategy for hemicelluloses• Value-added/ODMT wood in biorefineries• Projects at HUT• Conclusions
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Inflation Corrected Price of Northern Bleached Softwood Kraft Pulp
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Pulp/Paper Capital Spending in N.A.
Facilities are not maintained below 75% expenditures(Kinstrey,R, Pulp and Paper. January 2004)
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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
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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
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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
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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
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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
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Pulping Benefits of Hemicellulose Extraction
– Decreased alkali consumption– Reduced organic + inorganic load to
recovery– Increased delignification rate– Increased pulp production rate
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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 ($500/MT) into ethanol
• Cellulose has high crystallinity, is durable and has unique structural properties
Pulp is more valuable than ethanol. Keeppulp as product in paper or structural products
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Fuel Costs in Forest BiorefineryFuel Heating Value
(GJ/MT)Fuel Cost
(US$/Dry MT)Energy Cost
(US$/GJ)
Oil 43.5 555(US$60/barrel)
11.8
Biomass(20% moisture)
15 55 3.7
Black Liquor (20% moisture)
12.6 75 x 3/4 = 56(org/inorg = 3/1)
4.4
Lignin 26.9 75 2.8Carbohydrates 13.6 75 5.5
•Do not use oil!•Obtain energy from biomass and/or black liquor!•Minimize use of carbohydrates for energy purposes
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Wood Extraction
Biomass(bark, etc.)
Solid Wood
Wood Fiber
Raw WoodExtract
Alkaline Pulping
OxygenDelignification
Pulp Bleaching
BleachedPulp
BlackLiquor
Black Liquorgasification
ElectricPower
HighPressureSteam
White Liquor(NaOH +
AQ)
Wood Modification
Wood ExtractConversion
Sugar-based
Polymers
WoodExtractFiltrate
CarbonFibers
WoodComposite
Biomass Gasifier Power +Steam
NaOH
Trees
SynthesisGas Diesel Fuel
Ethanol
IFPRIFPR
Existing Products
Existing Processes
New Processes
=
=
=
Legend
= Νεω Προδυχτσ
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Hemicellulose Conversion Strategy
• Produce oxygen containing products to increase yield, shorten conversion path and competitiveness relative to petroleum-based
• Thus, produce alcohols, carboxylic acids, lactones, and esters
• Bio and catalytic conversions must work for both C5 and C6 sugars
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Maximizing ValueProduct Price ($/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
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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
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Projects at HUT
• Extraction Kinetics of Hemicelluloses
• High Temperature Degradation Kinetics of Black Liquor in the Liquid Phase
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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
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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
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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.
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Setup at UMaine
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Collaborations?
• Antti Grönroos, VTT Jyvaskyla• Pertti Koukkari, VTT Espoo• Liisa Viikari, University of Helsinki• Kari Saviharju, Andritz Oy• Others?
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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
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Collaborations?
• Pat McKeough, VTT Jyvaskyla• Raimo Alen, University of Jyvaskyla• Carl-Johan Fogelholm, HUT• Miko Hupa, Abo Akademi• Kari Saviharju, Andritz Oy• Others?
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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:
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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
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What Products?(Mike Pacheco, NREL)
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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