Utilization of Fractionated Bio-Oil in AsphaltMohamed Abdel Raouf Monday, March 28, 2011. GCMS of...

Utilization of FractionatedBio-Oil in Asphalt

R. Christopher WilliamsJustinus SatrioMarjorie Rover

Robert C. BrownSheng Teng

Monday, March 28, 2011

Presentation Outline

Background Bio-oil pilot plant production Experimental Plan Results Conclusions and Future Work


Societal Issues

Economy Transportation fuel pricing Job creation Infrastructure funding & renewal Energy independence Climate change


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


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


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


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


Bio-Energy Components

Corn Based Ethanol (wet & dry mill) Cellulosic Ethanol Bio-diesel Bio-oil (non-food source)


Bio-oil Pilot Plant


Bio-Oil


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%


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


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


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)


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)



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


Micropyrolyzer GC/MS Analysis of Feedstock Materials

Oak Wood

Switch Grass

Corn Stover


GC/MS Analysis of ESP Fractions

Oak Wood

Switch Grass

Corn Stover


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


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


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%)


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


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


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*)


Institute for Transportation

Development of Non-Petroleum Based Binders for Use in Flexible Pavements

R. Christopher WilliamsMohamed Abdel Raouf


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





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


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


15-N5 0.00000 0.20047

Blend 15

15-N6 0.00000 0.17793


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-


Viscosity-Temperature Susceptibility


Effect of Shear Rate on Viscosity


Arrhenius Model for AAM


Arrhenius Model for AAD


Arrhenius Model for Blend 1









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


Secondary Charcoal Generation


Secondary Charcoal Generation


Nature, Vol. 442, 10 Aug 2006

Bio-char: Soil amendment & carbon


*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

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


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.


Moving Forward

• Laboratory mix performance• Scale up of production facilities• Substantial capital investment• Multiple end markets for pyrolysis

products• Demonstration projects


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


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


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


Thank You!

&Questions?


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Utilization of Fractionated Bio-Oil in AsphaltMohamed Abdel Raouf Monday, March 28, 2011. GCMS of...

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