utilization of fractionated bio-oil in asphaltmohamed abdel raouf monday, march 28, 2011. gcms of...
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Utilization of FractionatedBio-Oil in Asphalt
R. Christopher WilliamsJustinus SatrioMarjorie Rover
Robert C. BrownSheng Teng
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Presentation Outline
Background Bio-oil pilot plant production Experimental Plan Results Conclusions and Future Work
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Societal Issues
Economy Transportation fuel pricing Job creation Infrastructure funding & renewal Energy independence Climate change
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Asphalt IndustryBackground & Challenges
Approximately 68% of GDP utilizes our transportation systems
About 90% of Nation’s paved highways use asphalt Asphalt pavements and composite pavements Maintenance applications (patching, crack sealing, surface
treatments)
Asphalt is derived from crude petroleum
Refinery modifications has removed asphalt from the market to produce more transportation fuels
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Impacts of Higher Crude Oil Prices
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
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Asphalt Paving Industry Market
Nationally 500 million tons of hot mix asphalt ($30 billion
annually)
30 million liquid tons of asphalt ($21 billion annually)
~4,000 stationary & 500 mobile hot mix asphalt plants
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Bio-economy & Transportation Link Market share of bio-energy will become greater
percentage of overall energy sector
Opportunities for utilizing bio-energy co-products exist in asphalt industry
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Bio-Energy Components
Corn Based Ethanol (wet & dry mill) Cellulosic Ethanol Bio-diesel Bio-oil (non-food source)
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Bio-oil Pilot Plant
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Bio-Oil
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Bio-oil production efficiency & cost
Energy efficiency 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%
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Products Generated from Bio-Oil
Biomass pyrolyzed to bio-oil Bio-oil fractions converted to renewable fuel, asphalt, and
other products
Pyrolyzer
Sugars Phenols Acids
Fuel Asphalt Co-‐Products
Biomass
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Characteristics of Fractionated Bio-Oil
Property Cond. 1 Cond. 2 Cond. 3 Cond. 4 ESPFraction of total oil (wt%)pHViscosity @40oC (cSt)Lignin Content (wt%)Water Content (wt%)C/H/O Molar Ratio
6-
SolidHighLow
1/1.2/ 0.5
223.5149329.3
1/ 1.6/ 0.6
372.72.25.046
1/ 2.5 / 2
152.52.62.646
1/ 2.5 /1.5
203.3543503.3
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 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
Biomass
Monomers/Isomers
Low Mol.Wt SpeciesRing-opened Chains
H+
H+
M+ M+
AerosolsHigh MW Species
Gases/Vapors
Thermo-mechanical
Ejection
Vaporization
Molten BiomassT ~ 430oC
(dT/dt)→∞
CO + H2
Synthesis GasReforming
TM+
Volatile Products
M+ : Catalyzed by Alkaline CationsH+ : Catalyzed by AcidsTM+ : Catalyzed by Zero Valent Transition Metals
(Observed at very high heating rates)
OligomersSource: Raedlin (1999)
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Corn stover (0.5-1.0mm)10 run average, different conditionsσbio-oil = 6.09%; σchar= 8.27%
Corn fiber (1.0 mm)2 run average, same conditionsσbio-oil = 1.33%; σchar= 0.148%
Red oak (0.75 mm)6 run average, different conditionsσbio-oil = 2.21%; σchar= 1.89%
37%30%
33%
Bio-oil Biochar Gas Unaccounted
*Auger pyrolyzer, ISU (2008)
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Characteristics of Bio-oil Fractions
Property Cond. 1 Cond. 2 Cond. 3 Cond. 4 ESP
Frac%on of total oil (wt%)
pH
Viscosity @40oC (cSt)
Lignin Content (wt%)
Water Content (wt%)
C/H/O Molar Ra%o
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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Micropyrolyzer GC/MS Analysis of Feedstock Materials
Oak Wood
Switch Grass
Corn Stover
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GC/MS Analysis of ESP Fractions
Oak Wood
Switch Grass
Corn Stover
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Experimental Plan 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 Corn Stover Oak Wood Switch Grass
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Experimental Plan
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 TypesCorn Stover
AAD-1 AAM-1 LPMBBio-oil TypesCorn 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%)
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Asphalts Used in Research
Component
CompositionAAD-1 AAM-1
Elemental
CompositionAAD-1 AAM-1
Asphaltenes 23.9 9.4 Carbon 81.6 86.8
Polar aromatics 41.3 50.3 Hydrogen 10.8 11.2
Napthene aromatics 25.1 41.9 Oxygen 0.9 0.5
Saturates 8.6 1.9 Sulfur 6.9 1.2
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Performance Testing1. Blend asphalt and lignin in a high speedshear mill at 145°C for 15 minutes
2. Evaluate high-temperaturerheological 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-temperaturerheological properties of RTFOaged blends with a DSR
6. Evaluate inter-temperaturerheological properties of PAVaged blends with a DSR
7. Evaluate low-temperaturerheological properties of unaged blends with a BBR
8. Calculatecontinuous performance grade of mixtures
9. Compare results of different asphalt/bio oilblends
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Findings 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*)
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Institute for Transportation
Development of Non-Petroleum Based Binders for Use in Flexible Pavements
R. Christopher WilliamsMohamed Abdel Raouf
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GCMS of Bio-oils 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
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Blend # Sample ID Weight (%) Weight (%)Blend # Sample ID Furfural Phenol
Blend 1
1-N1 0.06670 0.08894
Blend 1
1-N2 0.04449 0.08899
Blend 1 1-N3 0.04448 0.06672Blend 1 1-N4 0.00000 0.04452Blend 1
1-N5 0.00000 0.04443
Blend 1
1-N6 0.00000 0.04443
Blend 8
8-N1 0.04443 0.26661
Blend 8
8-N2 0.02205 0.17642
Blend 8 8-N3 0.02283 0.22827Blend 8 8-N4 0.00000 0.09007Blend 8
8-N5 0.00000 0.13393
Blend 8
8-N6 0.00000 0.11109
Blend 15
15-N1 0.02238 0.38042
Blend 15
15-N2 0.02224 0.40026
Blend 15 15-N3 0.00000 0.37784Blend 15 15-N4 0.00000 0.24449Blend 15
15-N5 0.00000 0.20047
Blend 15
15-N6 0.00000 0.17793
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Gas Chromatograph Mass Spectometry
1,6-Anhydro-á-D-glucopyranose (levogluco) 2(5H)-Furanone, 3-methyl- 2,4-Dimethylphenol 2-Furanmethanol 2-Propanone, 1-hydroxy- 4 methyl 2,6 dimethoxy phenol Furfural Hydroquinone Phenol Phenol, 2,5-dimethyl- Phenol, 2,6-dimethoxy- Phenol, 2-ethyl- Phenol, 2-methoxy-4-methyl- Phenol, 2-methyl- Phenol, 3,4-dimethyl- Phenol, 3-ethyl- Phenol, 3-methyl-
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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
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Arrhenius Model for Blend 1
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Arrhenius Model for Blend 2
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Arrhenius Model for Blend 4
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Moisture Sensitivity Test Results
Mix ID TreatmentPeak Force
(kN)Thickness(mm)
Tensile Strength(Pa)
Tensile Strength(psi)
AverageTensile Strength
TSR
0-‐1 Cond. 4.904 62.5 499.5 72.4
73.4
95.9
0-‐2 Cond. 4.945 62.5 503.7 73.073.4
95.9
0-‐3 Cond. 5.029 62.5 512.2 74.373.4
95.90-‐4 Cond. 4.999 62.5 509.2 73.8
73.4
95.90-‐5 Uncond. 5.130 62.5 522.5 75.8
76.5
95.9
0-‐6 Uncond. 5.201 62.5 529.8 76.876.5
95.9
0-‐7 Uncond. 5.197 62.5 529.4 76.876.5
95.9
0-‐8 Uncond. 5.198 62.5 529.5 76.8
76.5
95.9
1-‐1 Cond. 5.162 62.5 525.8 76.2
75.9
98.8
1-‐2 Cond. 5.165 62.5 526.1 76.375.9
98.8
1-‐3 Cond. 5.148 62.5 524.4 76.075.9
98.81-‐4 Cond. 5.081 62.5 517.5 75.0
75.9
98.81-‐5 Uncond. 5.187 62.5 528.3 76.6
76.8
98.8
1-‐6 Uncond. 5.200 62.5 529.7 76.876.8
98.8
1-‐7 Uncond. 5.206 62.5 530.3 76.976.8
98.8
1-‐8 Uncond. 5.213 62.5 531.0 77.0
76.8
98.8
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Secondary Charcoal Generation
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Secondary Charcoal Generation
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Nature, Vol. 442, 10 Aug 2006
Bio-char: Soil amendment & carbon
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*However, biochar quality is very important. The wrong type of biochar can cause yield decreases!
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.
Plant Population on 6/24/08(Seeding rate 30000)
Corn yield 2008 (56 total plots)
First year trials in Iowa showed a 15% increase plant populations, and a 4% increase in corn grain yield from biochar applications.*
Laird et al.Monday, March 28, 2011
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Car
bon
Stor
ed (l
b/ac
re/y
r)
Greenhouse gases reduced by carbon storage in agricultural
soils
0
500.000
1000.000
1500.000
2000.000
Pyrolytic CharNo-Till SwitchgrassNo-Till CornPlow-Tilled CornChar from pyrolyzing one-half of corn stover
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Summary
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.
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Moving Forward
• Laboratory mix performance• Scale up of production facilities• Substantial capital investment• Multiple end markets for pyrolysis
products• Demonstration projects
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Big Picture
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
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The Developing Bio-Energy Sector 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
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Thanks & Acknowledgements 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
Mark Dunn & Sandra Larson Scott Schram, John Hinrichsen & Jim Berger
Asphalt Paving Association of Iowa
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Thank You!
&Questions?
Monday, March 28, 2011