Utilization of Fractionated
Bio-Oil in Asphalt
R. Christopher Williams
Justinus Satrio
Marjorie Rover
Robert C. Brown
Sheng Teng
Monday, March 28, 2011
Presentation Outline
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Background
Bio-oil pilot plant production
Experimental Plan
Results
Conclusions and Future Work
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Societal Issues
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Economy
Transportation fuel pricing
Job creation
Infrastructure funding & renewal
Energy independence
Climate change
Monday, March 28, 2011
Asphalt Industry
Background & Challenges
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Approximately 68% of GDP utilizes our transportation
systems
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About 90% of Nation’s paved highways use asphalt
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Asphalt pavements and composite pavements
Maintenance applications (patching, crack sealing, surface
treatments)
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Asphalt is derived from crude petroleum
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Refinery modifications has removed asphalt from the
market to produce more transportation fuels
Monday, March 28, 2011
Impacts of Higher Crude Oil
Prices
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Higher asphalt & fuel prices reduces the number of
infrastructure projects
Fewer miles driven
 50 billion fewer miles from November 2007 to May 2008
 11 billion fewer comparing March 2007 to March 2008
(4.3% decrease)
 15 billion fewer miles comparing August 2007 to August
2008 (5.6% decrease)
Decrease in highway tax revenue
Less asphalt polymers (butadiene) available due to change
in polymer production and reduction in tire manufacturing
Less money for infrastructure projects
Monday, March 28, 2011
Asphalt Paving Industry
Market
Nationally
 500 million tons of hot mix asphalt ($30 billion
annually)
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30 million liquid tons of asphalt ($21 billion annually)
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~4,000 stationary & 500 mobile hot mix asphalt
plants
Monday, March 28, 2011
Bio-economy & Transportation
Link
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Market share of bio-energy will become greater
percentage of overall energy sector
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Opportunities for utilizing bio-energy co-products exist in
asphalt industry
Monday, March 28, 2011
Bio-Energy Components
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Corn Based Ethanol (wet & dry mill)
Cellulosic Ethanol
Bio-diesel
Bio-oil (non-food source)
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Bio-oil Pilot Plant
Monday, March 28, 2011
Bio-Oil
Monday, March 28, 2011
Bio-oil production efficiency & cost
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Energy efficiency
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Conversion to 75 wt-% bio-oil translates to
energy efficiency of 70%
If carbon used for energy source (process
heat or slurried with liquid) then efficiency
approaches 94%
Monday, March 28, 2011
Products Generated from BioOil
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Biomass pyrolyzed to bio-oil
Bio-oil fractions converted to renewable fuel, asphalt, and
other products
Biomass
Pyrolyzer
Monday, March 28, 2011
Sugars
Phenols
Acids
Fuel
Asphalt
Co-­‐Products
Characteristics of Fractionated BioOil
Property
Cond. 1
Cond. 2
Cond. 3
Cond. 4
ESP
Fraction of total oil (wt%)
pH
Viscosity @40oC (cSt)
Lignin Content (wt%)
Water Content (wt%)
C/H/O Molar Ratio
6
Solid
High
Low
1/1.2/ 0.5
22
3.5
149
32
9.3
1/ 1.6/ 0.6
37
2.7
2.2
5.0
46
1/ 2.5 / 2
15
2.5
2.6
2.6
46
1/ 2.5 /1.5
20
3.3
543
50
3.3
1/1.5/ 0.5
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Fast pyrolysis - rapid thermal decomposition of organic
compounds in the absence of oxygen to produce gas, char,
and liquids
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Liquid yields as high as 78% are possible for relatively short residence
times (0.5 - 2 s), moderate temperatures (400-600 oC), and rapid
quenching at the end of the process
(Observed at very
high heating rates)
(dT/dt)→∞
Biomass
M+
H+
Molten
Biomass
T ~ 430oC
Oligomers
H+
M+ Monomers/
Isomers
Low Mol.Wt
Species
Ring-opened
Chains
Monday, March 28, 2011
M+ : Catalyzed by Alkaline Cations
H+ : Catalyzed by Acids
TM+ : Catalyzed by Zero Valent Transition Metals
Thermomechanical
Ejection
Aerosols
High MW
Species
Source: Raedlin (1999)
CO + H2
Vaporization
Gases/Vapors
Reforming
TM+
Synthesis Gas
Volatile Products
Bio-oil
30%
Biochar Gas
Unaccounted
37%
33%
Corn stover (0.5-1.0mm)
Corn fiber (1.0 mm)
Red oak (0.75 mm)
10 run average, different conditions2 run average, same conditions 6 run average, different conditions
σbio-oil = 6.09%; σchar= 8.27%
σbio-oil = 2.21%; σchar= 1.89%
σbio-oil = 1.33%; σchar= 0.148%
*Auger pyrolyzer, ISU (2008)
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Monday, March 28, 2011
Characteristics of Bio-oil
Fractions
Property
Cond. 1
Cond. 2
Cond. 3
Cond. 4
ESP
Frac%on of total oil (wt%)
6
22
37
15
20
pH
-­‐
3.5
2.7
2.5
3.3
Viscosity @40oC (cSt)
Solid
149
2.2
2.6
543
Lignin Content (wt%)
High
32
5.0
2.6
50
Water Content (wt%)
Low
9.3
46
46
3.3
C/H/O Molar Ra%o
Monday, March 28, 2011
1/1.2/ 0.5 1/ 1.6/ 0.6
1/ 2.5 / 2
1/ 2.5 /1.5 1/1.5/ 0.5
Micropyrolyzer GC/MS Analysis of
Feedstock Materials
Oak Wood
Switch Grass
Corn Stover
Monday, March 28, 2011
GC/MS Analysis of ESP
Fractions
Oak Wood
Switch Grass
Corn Stover
Monday, March 28, 2011
Experimental Plan
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Three asphalt binders
 1 local binder (1 polymer-modified, 1 neat binder)
 2 well known binders (AAD-1 & AAM-1)
Three experimental bio-oil fractions
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Corn Stover
Oak Wood
Switch Grass
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Experimental Plan
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Each asphalt mixed with each bio-oil sample at 3,
6, and 9 percent by weight
Evaluate rheological properties and determine Tc
and performance grade of each blend
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Bio-oil & Asphalt Experimental
Factors
Bio-oil Types
AAD-1
AAM-1
LPMB
Corn Stover
0,3,6,9 (wt%)
0,3,6,9 (wt%)
0,3,6,9 (wt%)
Oak Wood
3,6,9 (wt%)
3,6,9 (wt%)
3,6,9 (wt%)
Switch Grass
3,6,9 (wt%)
3,6,9 (wt%)
3,6,9 (wt%)
Monday, March 28, 2011
Asphalts Used in Research
Component
Elemental
AAD-1
AAM-1
Asphaltenes
23.9
9.4
Polar aromatics
41.3
Napthene aromatics
Saturates
Composition
Monday, March 28, 2011
AAD-1
AAM-1
Carbon
81.6
86.8
50.3
Hydrogen
10.8
11.2
25.1
41.9
Oxygen
0.9
0.5
8.6
1.9
Sulfur
6.9
1.2
Composition
Performance Testing
1. Blend asphalt and
lignin in a high speed
shear mill at 145°C
for 15 minutes
6. Evaluate inter-temperature
rheological properties of PAV
aged blends with a DSR
7. Evaluate low-temperature
rheological properties of
unaged blends with a BBR
Monday, March 28, 2011
2. Evaluate high-temperature
rheological properties of
unaged blends with a DSR
3. Short-term age
asphalt/lignin
blends with a RTFO
5. Long-term age
asphalt/lignin
blends with a PAV
4. Evaluate high-temperature
rheological properties of RTFO
aged blends with a DSR
8. Calculate
continuous performance
grade of mixtures
9. Compare results of
different asphalt/bio oil
blends
Findings
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The addition of fractionated bio-oil to asphalt
binders causes a stiffening effect
 Binder effects, biomass source of bio-oil, and
amount of fractionated bio-oil
The stiffening effect increases the high, int., and
low critical temperatures of the asphalt/lignin
blends
The high temperatures are increased more than
the low temperatures
Grade ranges in some combinations are increased
by one grade (6ºC) and in other combinations no
effects
Mix tests show beneficial effects of using bio-oil
in asphalt (E*)
Monday, March 28, 2011
Institute for Transportation
Development of Non-Petroleum Based
Binders for Use in Flexible Pavements
R. Christopher Williams
Mohamed Abdel Raouf
Monday, March 28, 2011
GCMS of Bio-oils
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Oak Wood (B1), Switch Grass (B8), Corn Stover (B15)
N1: Unaged
N2: Heat Treated at 120C for 2 hours
N3: Heat Treated + RTFO at 120C for 10 min.
N4: Heat Treated + RTFO at 120C for 20 min.
N5: Heat Treated + RTFO at 120C for 30 min.
N6: Heat Treated + RTFO 20 min + PAV at 110C, 2.1MPa,
2.5 hours
Monday, March 28, 2011
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Blend #
Blend 1
Blend 8
Blend 15
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Sample ID
1-N1
1-N2
1-N3
1-N4
1-N5
1-N6
8-N1
8-N2
8-N3
8-N4
8-N5
8-N6
15-N1
15-N2
15-N3
15-N4
15-N5
15-N6
Weight (%)
Furfural
Phenol
0.06670
0.08894
0.04449
0.08899
0.04448
0.06672
0.00000
0.04452
0.00000
0.04443
0.00000
0.04443
0.04443
0.26661
0.02205
0.17642
0.02283
0.22827
0.00000
0.09007
0.00000
0.13393
0.00000
0.11109
0.02238
0.38042
0.02224
0.40026
0.00000
0.37784
0.00000
0.24449
0.00000
0.20047
0.00000
0.17793
Gas Chromatograph Mass
Spectometry
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1,6-Anhydro-á-D-glucopyranose (levogluco)
2(5H)-Furanone, 3-methyl2,4-Dimethylphenol
2-Furanmethanol
2-Propanone, 1-hydroxy4 methyl 2,6 dimethoxy phenol
Furfural
Hydroquinone
Phenol
Phenol, 2,5-dimethylPhenol, 2,6-dimethoxyPhenol, 2-ethylPhenol, 2-methoxy-4-methylPhenol, 2-methylPhenol, 3,4-dimethylPhenol, 3-ethylPhenol, 3-methyl-
Monday, March 28, 2011
Viscosity-Temperature
Susceptibility
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Effect of Shear Rate on Viscosity
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Arrhenius Model for AAM
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Arrhenius Model for AAD
Monday, March 28, 2011
Arrhenius Model for Blend 1
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Arrhenius Model for Blend 2
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Arrhenius Model for Blend 4
Monday, March 28, 2011
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Moisture Sensitivity Test Results
Mix ID
Peak Force Thickness
Treatment
(kN)
(mm)
0-­‐1
0-­‐2
0-­‐3
0-­‐4
0-­‐5
0-­‐6
0-­‐7
0-­‐8
1-­‐1
1-­‐2
1-­‐3
1-­‐4
1-­‐5
1-­‐6
1-­‐7
1-­‐8
Monday, March 28, 2011
Cond.
Cond.
Cond.
Cond.
Uncond.
Uncond.
Uncond.
Uncond.
Cond.
Cond.
Cond.
Cond.
Uncond.
Uncond.
Uncond.
Uncond.
4.904
4.945
5.029
4.999
5.130
5.201
5.197
5.198
5.162
5.165
5.148
5.081
5.187
5.200
5.206
5.213
62.5
62.5
62.5
62.5
62.5
62.5
62.5
62.5
62.5
62.5
62.5
62.5
62.5
62.5
62.5
62.5
Tensile Strength
(Pa)
499.5
503.7
512.2
509.2
522.5
529.8
529.4
529.5
525.8
526.1
524.4
517.5
528.3
529.7
530.3
531.0
Tensile Strength
(psi)
72.4
73.0
74.3
73.8
75.8
76.8
76.8
76.8
76.2
76.3
76.0
75.0
76.6
76.8
76.9
77.0
Average
Tensile Strength
TSR
73.4
95.9
76.5
75.9
98.8
76.8
Secondary Charcoal Generation
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Secondary Charcoal Generation
Monday, March 28, 2011
Bio-char: Soil amendment & carbon
Nature, Vol. 442, 10 Aug 2006
Monday, March 28, 2011
Several studies have reported
large increases in crop yields
from the use of biochar as a soil
amendment. However, most of
these studies were conducted in
the tropics on low fertility soils.
Need to study how temperate
region soils will respond to
biochar amendments.
First year trials in Iowa showed a
15% increase plant populations,
and a 4% increase in corn grain
yield from biochar applications.*
Plant Population on 6/24/08
(Seeding rate 30000)
Corn yield 2008
(56 total plots)
*However, biochar quality is very
important. The wrong type of biochar
can cause yield decreases!
Laird et al.
Monday, March 28, 2011
Carbon Stored (lb/acre/yr)
Greenhouse gases reduced by
carbon storage in agricultural
soils
2000.000
1500.000
1000.000
500.000
0
Pyrolytic Char
No-Till Switchgrass
No-Till Corn
Plow-Tilled Corn
Char from pyrolyzing one-half of corn
stover
Monday, March 28, 2011
Summary
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Bio asphalt has similar temperature sensitivity to
petroleum derived asphalt.
The temperature range for the bio-oil and
bitumen blends were different.
An asphalt derived from biomass has been
developed that behaves like a viscoelastic
material just like petroleum derived asphalt.
The bio asphalt can be produced locally
The production process sequesters greenhouse
gases.
Monday, March 28, 2011
Moving Forward
• Laboratory mix performance
• Scale up of production facilities
• Substantial capital investment
• Multiple end markets for pyrolysis
products
• Demonstration projects
Monday, March 28, 2011
Big Picture
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Economic opportunity
Integration of green technologies into asphalt
industry that is sustainable
Bio-energy co-products will be regionally
produced and “married” with regionally
supplied asphalt binders
The US economy is highly dependant upon
transportation infrastructure
Monday, March 28, 2011
The Developing Bio-Energy
Sector
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Crude oil, asphalt & polymer price increases
US energy independence
Sequestering greenhouse gases
Utilizing bio-energy components to replace
crude oil sources
In the future, the bio-energy sector will
become a larger portion of the total energy
sector
Biopolymers- alternatives to butadiene
Monday, March 28, 2011
Thanks & Acknowledgements
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Iowa Highway Research Board
InTrans (Judy Thomas, Sabrina Shields-Cook)
Center for Sustainable Environmental
Technology (Robert Brown, Sam Jones, Marge
Rover)
Iowa Energy Center (Bill Haman)
Iowa Department of Transportation
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Mark Dunn & Sandra Larson
Scott Schram, John Hinrichsen & Jim Berger
Asphalt Paving Association of Iowa
Monday, March 28, 2011
Thank
You!
&
Questions?
Monday, March 28, 2011