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Bioasphalt and Biochar from Pyrolysis of Urban Yard Waste by Daniel R

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Bioasphalt and Biochar from Pyrolysis of Urban Yard Waste by Daniel R Bioasphalt and Biochar from Pyrolysis of Urban Yard Waste by Daniel R. Hill Submitted in partial fulfillment of the requirements for the degree of Master of Science Department of Civil Engineering Case Western Reserve University January 2012 CASE WESTERN RESERVE UNIVERSITY SCHOOL OF GRADUATE STUDIES We hereby approve the thesis/dissertation of _Daniel R. Hill__________________________________________ candidate for the _Master of Science________________degree*. (signed)_Aaron A. Jennings________________________________ (chair of the committee) _David Zeng_____________________________________ _Xiong “Bill” Yu__________________________________ ________________________________________________ (date) _4 August 2011_________________ *We also certify that written approval has been obtained for any proprietary material contained therein. ii Table of Contents List of Tables……………………………………………………………………………..iii List of Figures……………………………………………………………………………..v Acknowledgements……………………………………………………………………..viii Abstract…………………………………………………………………………………...ix 1. Introduction ......................................................................................................................2 2.1. Recent Interest in Pyrolysis as a Sustainable Technology ....................................... 3 2.2. Desirability of Non-Petroleum-Based Asphalt Binders ......................................... 10 2. Literature Review...........................................................................................................12 2.1. Yard Waste Generation and Management.............................................................. 12 Generation and Current Management……………………………………………….12 Greenhouse Gas Emissions and Carbon Storage……………………………………13 Issues in Yard Waste Composting…………………………………………………..14 2.2. Pyrolysis ................................................................................................................. 16 Slow Pyrolysis………………………………………………………………………17 Fast Pyrolysis………………………………………………………………………..17 Reactor Types……………………………………………………………………….18 2.3. Biochar ................................................................................................................... 23 Properties of Biochar………………………………………………………………..23 Carbon Sequestering Potential of Biochar…………………………………………..25 Added Environmental Benefits of Biochar…………………………………………26 2.4. Bio-Oil .................................................................................................................... 27 Chemical Properties of Bio-Oil……………………………………………………..27 Physical Properties of Bio-Oil………………………………………………………29 Applications of Pyrolysis Liquids…………………………………………………..30 2.5. Asphalt Binder Properties and Testing Procedures ................................................ 35 Rheological Properties of Binders…………………………………………………..35 Pavement Deformations Related to Binder Rheology………………………………37 Testing and Specifications for Binders……………………………………………...38 Specifications for Asphalt Binders in Ohio…………………………………………43 Testing on Bio-Oil…………………………………………………………………..44 3. Materials and Methods ...................................................................................................44 4.1. Sample Collection .................................................................................................. 44 4.2. Sample Preparation ................................................................................................ 47 4.3. Testing Methods ..................................................................................................... 49 Drying……………………………………………………………………………….49 Pyrolysis…………………………………………………………………………….51 Chemical Evaluation of Condensate………………………………………………...59 4. Results and Discussion ..................................................................................................64 5. Summary and Conclusions ............................................................................................75 iii 6. Appendix ........................................................................................................................79 6.1. Appendix A: Methods and Results of Growth Experiments .................................. 79 Experiment 1 - Soybeans……………………………………………………………79 Experiment 2 – Corn………………………………………………………………...82 Experiment 3 – Soybeans…………………………………………………………...84 6.2. Appendix B: Ohio Asphalt Binder Specifications ................................................. 88 7. References ......................................................................................................................90 iv List of Tables Table 1: Example Organizations Promoting Biochar Use .................................................. 6 Table 2: Moisture and Pyrolysis Testing Results for All Samples ................................... 64 Table 3: Moisture and Pyrolysis Testing Results for Branch Samples ............................. 66 Table 4: Moisture and Pyrolysis Testing Results for Leaf Samples ................................. 66 Table 5: Evaluation of Pre-Drying Effect on Yields and Byproduct Collection .............. 68 Table 6: Preliminary Chemical Analysis of Off-Gas Condensate .................................... 74 Table 7: Yield Results from First Biochar Growth Experiment with Soybeans............... 79 Table 8: Yield Results from Second Biochar Growth Experiment with Corn ................. 82 Table 9: Yield Results from Third Biochar Growth Experiment with Beans................... 85 v List of Figures Figure 1: Nutrient Poor Oxisol (left) and Terra Preta Oxisol (right) .................................. 4 Figure 2: Terra Preta Formations Discovered in Brazil ...................................................... 5 Figure 3: Initial Bench Scale Pyrolysis Reactor Setup ....................................................... 7 Figure 4: Soybean Plants in Biochar Growth Experiments ................................................ 8 Figure 5: Corn Plants in Biochar Growth Experiments ...................................................... 9 Figure 6: Schematic of Fluidized Bed Reactor ................................................................. 19 Figure 7: A Rolling Thin Film Oven ................................................................................ 42 Figure 8: Pressure Aging Vessel ....................................................................................... 43 Figure 9: Yard Waste in Biodegradable Bags ................................................................... 46 Figure 10: Yard Waste Brush Pile (Oak Branches) .......................................................... 47 Figure 11: Yard Waste Log Pile ....................................................................................... 47 Figure 12: Rhododendron Leaves Prepared for Pyrolysis ................................................ 48 Figure 13: Oak Branches Prepared for Pyrolysis .............................................................. 49 Figure 14: Dried Willow Branches ................................................................................... 50 Figure 15: Dried Black Locust Leaves ............................................................................. 50 Figure 16: Pyrolysis Reactor Connected to Discharge Piping in Furnace ........................ 52 Figure 17: Heated Piping Directing Off-Gases into Collection Flask .............................. 52 Figure 18: Second Collection Flask and Water-Cooled Condensers ................................ 53 Figure 19: Schematic of Pyrolysis Reactor and Collection System ................................. 53 Figure 20: Second Collection Flask Filled with Dense Off-Gases ................................... 55 Figure 21: Maple Branches Before Pyrolysis ................................................................... 55 Figure 22: Maple Branches After Pyrolysis (Char) .......................................................... 56 Figure 23: Maple Samaras Before Pyrolysis .................................................................... 56 vi Figure 24: Maple Samaras After Pyrolysis (Char) ........................................................... 57 Figure 25: Off-Gases Concentrating in Glass Fittings Above First Collection Flask ...... 58 Figure 26: Setup of Boiling Reflux Flasks Under Condensers for COD Test .................. 61 Figure 27: Comparison of Byproduct Collection and Moisture Content .......................... 68 Figure 28: Byproduct Collection Over Project Duration .................................................. 69 Figure 29: Moisure Contents of Deciduous and Coniferous Samples .............................. 70 Figure 30: Organics Contents of Deciduous and Coniferous Samples ............................. 71 Figure 31: Bottled Pyrolytic Liquids ................................................................................ 73 Figure 32: Dry Soybean Stem Yield versus Char Levels in Soil ...................................... 81 Figure 33: Dry Bean Yield versus Char Levels in Soil .................................................... 81 Figure 34: Dry Plant Yield versus Biochar Levels in Soil ................................................ 83 Figure 35: Dry Plant Yield versus Topsoil Level in Pot ................................................... 84 Figure 36: Dry Bean Yield versus Biochar ....................................................................... 86 Figure 37: Dry Bean Yield versus Topsoil Addition Levels ............................................ 87 Figure 38: Dry Bean Yield versus Sand Addition Levels ................................................
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