Utilization of Fractionated Bio-Oil in Asphalt R. Christopher Williams Justinus Satrio Marjorie Rover Robert C. Brown Sheng Teng
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 Industry Background & 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 Biomass Pyrolyzer Sugars Phenols Acids Fuel Asphalt Co- Products
Characteristics of Fractionated Bio- Oil 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
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 o C), and rapid quenching at the end of the process (Observed at very high heating rates) (dt/dt) Molten Biomass T ~ 430 o C M + : Catalyzed by Alkaline Cations H + : Catalyzed by Acids TM + : Catalyzed by Zero Valent Transition Metals Biomass H + M + M + Oligomers H + Monomers/ Isomers Low Mol.Wt Species Ring-opened Chains Thermomechanical Ejection Vaporization Aerosols High MW Species Gases/Vapors Reforming TM + Volatile Products Source: Raedlin (1999) CO + H 2 Synthesis Gas
Bio-oil Biochar Gas Unaccounted 30% 37% 33% Corn stover (0.5-1.0mm) Corn fiber (1.0 mm) 10 run average, different conditions2 run average, same conditions σ bio-oil = 6.09%; σ char = 8.27% σ bio-oil = 1.33%; σ char = 0.148% Red oak (0.75 mm) 6 run average, different conditions σ bio-oil = 2.21%; σ char = 1.89% *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 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%)
Asphalts Used in Research Component Composition AAD-1 AAM-1 Elemental Composition AAD-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 Testing 1. Blend asphalt and lignin in a high speed shear mill at 145 C for 15 minutes 2. Evaluate high-temperature rheological properties of unaged blends with a DSR 3. Short-term age asphalt/lignin blends with a RTFO 6. Evaluate inter-temperature rheological properties of PAV aged blends with a DSR 5. Long-term age asphalt/lignin blends with a PAV 4. Evaluate high-temperature rheological properties of RTFO aged blends with a DSR 7. Evaluate low-temperature rheological properties of unaged blends with a BBR 8. Calculate continuous performance grade of mixtures 9. Compare results of different asphalt/bio oil blends
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 Williams Mohamed 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 # Blend 1 Blend 8 Blend 15 Sample ID Weight (%) Furfural Phenol 1-N1 0.06670 0.08894 1-N2 0.04449 0.08899 1-N3 0.04448 0.06672 1-N4 0.00000 0.04452 1-N5 0.00000 0.04443 1-N6 0.00000 0.04443 8-N1 0.04443 0.26661 8-N2 0.02205 0.17642 8-N3 0.02283 0.22827 8-N4 0.00000 0.09007 8-N5 0.00000 0.13393 8-N6 0.00000 0.11109 15-N1 0.02238 0.38042 15-N2 0.02224 0.40026 15-N3 0.00000 0.37784 15-N4 0.00000 0.24449 15-N5 0.00000 0.20047 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
Arrhenius Model for Blend 2
Arrhenius Model for Blend 4
Moisture Sensitivity Test Results Mix ID Treatment Peak Force (kn) Thickness (mm) Tensile Strength (Pa) Tensile Strength (psi) 0-1 Cond. 4.904 62.5 499.5 72.4 0-2 Cond. 4.945 62.5 503.7 73.0 0-3 Cond. 5.029 62.5 512.2 74.3 0-4 Cond. 4.999 62.5 509.2 73.8 0-5 Uncond. 5.130 62.5 522.5 75.8 0-6 Uncond. 5.201 62.5 529.8 76.8 0-7 Uncond. 5.197 62.5 529.4 76.8 0-8 Uncond. 5.198 62.5 529.5 76.8 1-1 Cond. 5.162 62.5 525.8 76.2 1-2 Cond. 5.165 62.5 526.1 76.3 1-3 Cond. 5.148 62.5 524.4 76.0 1-4 Cond. 5.081 62.5 517.5 75.0 1-5 Uncond. 5.187 62.5 528.3 76.6 1-6 Uncond. 5.200 62.5 529.7 76.8 1-7 Uncond. 5.206 62.5 530.3 76.9 1-8 Uncond. 5.213 62.5 531.0 77.0 Average Tensile Strength 73.4 76.5 75.9 76.8 TSR 95.9 98.8
Secondary Charcoal Generation
Secondary Charcoal Generation
Bio-char: Soil amendment & carbon Nature, Vol. 442, 10 Aug 2006
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.
Greenhouse gases reduced by carbon storage in agricultural Carbon Stored (lb/acre/yr) 2000.000 1500.000 1000.000 500.000 soils 0 Pyrolytic Char No-Till Switchgrass No-Till CornPlow-Tilled Corn Char 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?