Helsinki University of Technology
Innovative Forest Products
Biorefinery
Adriaan van Heiningen and Tapani Vuorinen
Helsinki University of Technology
Department of Forest Products Technology
Espoo, Finland
III Liekkipaiva
Espoo, January 31, 2007
Outline
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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
ÄTraditional forest products industry
needs more revenue from higher valueadded 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 LignoCellulosics
• 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 Undegraded
Hemicelluloses?
• 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 ($500/MT) into ethanol
• Cellulose has high crystallinity, is durable
and has unique structural properties
ÎPulp is more valuable than ethanol. Keep
pulp as product in paper or structural products
Fuel Costs in Forest Biorefinery
Fuel
Heating Value
(GJ/MT)
Fuel Cost
(US$/Dry MT)
Energy Cost
(US$/GJ)
43.5
555
(US$60/barrel)
11.8
Biomass
(20% moisture)
15
55
3.7
Black Liquor
(20% moisture)
12.6
75 x 3/4 = 56
(org/inorg = 3/1)
4.4
Lignin
26.9
75
2.8
Carbohydrates
13.6
75
5.5
Oil
•Do not use oil!
•Obtain energy from biomass and/or black liquor!
•Minimize use of carbohydrates for energy purposes
Biomass
(bark, etc.)
Power +
Steam
Biomass Gasifier
IFPR
Trees
Solid Wood
Wood Modification
Wood Fiber
Wood
Composite
Legend
Wood Extraction
Raw Wood
Extract
Synthesis
Gas
Diesel Fuel
High
Pressure
Steam
White Liquor
(NaOH +
AQ)
Alkaline Pulping
Black
Liquor
Black Liquor
gasification
Electric
Power
Carbon
Fibers
Oxygen
Delignification
Ethanol
NaOH
Pulp Bleaching
Wood Extract
Conversion
Wood
Extract
Filtrate
Sugarbased
Polymers
Bleached
Pulp
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Existing Products
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Existing Processes
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New Processes
= Νεω Προδυχτσ
Hemicellulose Conversion Strategy
• Produce oxygen containing products to
increase yield, shorten conversion path and
competitiveness relative to petroleum-based
• Thus, produce alcohols, carboxylic acids,
lactones, and esters
• Bio and catalytic conversions must work for
both C5 and C6 sugars
Maximizing Value
Present situation
Product
Pulp
Wood as fuel
Total
Price ($/ODMT)
500
55
Yield (%)
45
55
100
Value (US$/ODMT wood)
225
30
255
Value-Added: 255 – 75 = 180 US$/ODMT wood
Future Situation
Product
Pulp
Price
Wood Yield (%) Conversion (%) Value (US$/ODMT wood)
$500/ODMT
45
100
225
Polymer
$3000/MT
10
50
150
PU foam
$3000/MT
10
45
135
Diesel
$630/MT
35
40
88
$2.00/gallon
Total
100
Value-Added: 598 – 75 = 523 US$/ODMT wood
598
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
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Variables:
Wood type:
pH control:
Equipment:
Analysis:
T, t, pH, ultrasound
birch and pine
CO2/HCO3-/CO32- buffers
“Berty” type CSTR
- on-line UV and RI
- off-line TOC, TIC, TN, MeOH,
HAc, sugars
- extracted wood composition
- reducing ends in extracted wood
Berty CSTR
Cold Water
BFP
Flow Indicator
Heat Exchanger
UV
spectro.
280 ml Reactor
with a 100 ml basket
Heating
CO2
O2
Gas
Liquor tank
Computer
Domain Controller
Controller
Needle Valve
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?
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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
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Variables:
Black liquor:
Equipment:
Analysis:
T, t, pH
Pine kraft
Multiple small batch reactors
- Pressure
- Gas composition incl. TRS + NOx
- Liquor composition + properties
Collaborations?
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Pat McKeough, VTT Jyvaskyla
Raimo Alen, University of Jyvaskyla
Carl-Johan Fogelholm, HUT
Miko Hupa, Abo Akademi
Kari Saviharju, Andritz Oy
Others?
Conclusions
Benefits of Forest Biorefinery:
• 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 forestbased communities
Coproducts Pulp + Transportation Fluids
Pulp Production
Product
Price ($/ODMT) Yield (%)
Pulp
500
45
Wood fuel
55
55
Total
100
Value (US$/ODMT wood)
225
30
255
Value-Added: 255 – 75 = 180 US$/ODMT wood
Pulp and Transportation Fluids Coproduction
Product
Price
Wood Yield (%)
Conversion (%)
Value(US$/ODMTwood)
$500/ODMT
45
100
225
Ethanol
$670/ODMT
from hemi $2.00/gallon
10
43
29
Diesel
45
40
113
Pulp
Total
$630/ODMT
$2.00/gallon
100
Value-Added: 367 – 75 = 292 US$/ODMT wood
367
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