New Generation Bio-Binder Formulation

Transcription

1 Report # MATC-KSU: 261 Final Report WBS: New Generation Bio-Binder Formulation Stefan H. Bossmann, Ph.D.Ta Professor Department of Chemistry Kansas State University Hongwang Wang, Ph.D. Postdoctoral Research Associate Department of Chemistry Kansas State University Sebastian O. Wendel, Ph.D. Asanka S. Yapa Palamandadige K. Fernando Jose Covarrubias 2016 A Cooperative Research Project sponsored by U.S. Department of Transportation- Office of the Assistant Secretary for Research and Technology The contents of this report reflect the views of the authors, who are responsible for the facts and the accuracy of the information presented herein. This document is disseminated under the sponsorship of the Department of Transportation University Transportation Centers Program, in the interest of information exchange. The U.S. Government assumes no liability for the contents or use thereof.

2 New Generation Bio-Binder Formulation Stefan H. Bossmann, Ph.D.Ta Professor Department of Chemistry Kansas State University Hongwang Wang, Ph.D. Postdoctoral Research Associate Department of Chemistry Kansas State University Sebastian O. Wendel, Ph.D. Department of Chemical Engineering Kansas State University Asanka S. Yapa Department of Chemistry Kansas State University Palamandadige K. Fernando Kansas State University Jose Covarrubias Kansas State University A Report on Research Sponsored by Mid-America Transportation Center University of Nebraska-Lincoln May 2015

3 Technical Report Documentation Page 1. Report No. WBS# Government Accession No. 3. Recipient's Catalog No. 4. Title and Subtitle New Generation Bio-Binder Formulation 5. Report Date May Performing Organization Code 7. Author(s) Bossmann, S.; Wang, H.; Wendel, S.; Yapa, A.S.; Fernando, P.K.; and J. Covarrubias 9. Performing Organization Name and Address Mid-America Transportation Center 2200 Vine St. PO Box Lincoln, NE Sponsoring Agency Name and Address Research and Innovative Technology Administration University Transportation Centers Program Washington, DC USA 15. Supplementary Notes 8. Performing Organization Report No. WBS# Work Unit No. (TRAIS) 11. Contract or Grant No. 13. Type of Report and Period Covered July 2013 November Sponsoring Agency Code MATC TRB RiP No Abstract This research project is concerned with the utilization of waste materials from the production of renewable fuels for the production of low cost asphalt binders. The major obstacles to using renewable waste materials for asphalt production can be found in the relatively high water-solubility of these materials. In this project, mixtures of waste materials from the production of renewable fuels were subjected to heat treatment to make them more hydrophobic and facilitate better binding to asphalt components. 17. Key Words 18. Distribution Statement 19. Security Classif. (of this report) Unclassified 20. Security Classif. (of this page) Unclassified 21. No. of Pages Price ii

4 Table of Contents Project Scope...1 Materials Investigated...1 Lessons from Solubility Measurements...5 Sludge from Cellulose...5 Thermogravimetric Analysis...8 Summary...12 References...12 iii

5 List of Figures Figure 1 Solubility of the asphalt binder candidates derived from recycled materials...4 Figure 2 Doehlert Methodology for determining optical process conditions (amount of catalysts, reaction temperature, and reaction time)...7 Figure 3 Fe/Fe3O4-based acidic catalysts featuring a protective silica shell and sulfamic acid groups for acid-catalyzed degradation of cellulose...7 Figure 4 Solubility of the organic material resulting from cellulose degradation in four organic solvents...8 Figure 5 Thermogravimetric analysis (mass in mg vs. temperature in oc) of pure cellulose, cellulose sludge (10h of reaction at 170oC (see above)) and cellulose sludge (20h of reaction at 170oC). The heating rate was 5 degrees C per minute under nitrogen atmosphere...9 Figure 6 Thermogravimetric analysis (mass in mg vs. temperature in oc) Bio Oil (oil and solid separately), Cryo Rubber, Cryo GTR, and heat treated Bio Oil. The heating rate was 5 degrees C per minute under nitrogen atmosphere...10 Figure 7 Thermogravimetric analysis (mass in mg vs. temperature in oc) of Waste Glycerol from Emergent Green Energy Inc. The heating rate was 5 degrees C per minute under nitrogen atmosphere...11 iv

6 List of Tables Table 1 Solubility of candidates for asphalt binders derived from recycled resources...2 Table 2 Solubility of candidates for asphalt binders derived from recycled resources...3 v

7 Disclaimer The contents of this report reflect the views of the authors, who are responsible for the facts and the accuracy of the information presented herein. This document is disseminated under the sponsorship of the U.S. Department of Transportation s University Transportation Centers Program, in the interest of information exchange. The U.S. Government assumes no liability for the contents or use thereof. vi

8 Abstract This research project is concerned with the utilization of waste materials from the production of renewable fuels for the production of low cost asphalt binders. The major obstacles to using renewable waste materials for asphalt production can be found in the relatively high water-solubility of these materials. In this project, mixtures of waste materials from the production of renewable fuels were subjected to heat treatment to make them more hydrophobic and facilitate better binding to asphalt components. vii

9 Project Scope This research project is concerned with the utilization of waste materials from the production of renewable fuels for the production of low cost asphalt binders. The major obstacles to using renewable waste materials for asphalt production can be found in the relatively high water-solubility of these materials. In this project, mixtures of waste materials from the production of renewable fuels were subjected to heat treatment to make them more hydrophobic and facilitate better binding to asphalt components. Materials Investigated The following biomaterials and recycling products were investigated: 1) Cryo Rubber, Bio Oil, CryoGTR/MBO and heat-treated Bio Oil from Dr. Williams, Institute of Transportation, Iowa State University. 2) Waste cellulose residues from C6-sugar for ethanol production from Battelle Memorial Institute, Columbus, OH. 3) Waste glycerol from Emergent Green Energy Inc. 1.2MGY (SW Kansas Biodiesel Plant) Step 1 of this study consisted in determining the solubility of the materials in a variety of solvents with different log P (octanol/water partition coefficient): hexane (log P = 3.761), toluene (log P = 2.8), chloroform (log P = 2.0), ethanol (log P = ), water (log P = -3.26). The ideal bio-derived asphalt binder should be soluble in solvents with log P > 2, indicating possible association with the hydrophobic asphalt materials, but insoluble in solvents with log P < 2. Otherwise, the asphalt binder will be partially soluble in rain water. 1

10 Table 1 Solubility of candidates for asphalt binders derived from recycled resources Added sample weight Cryo Rubber Solvent Empty weight with label and lid Final weight Weight transfer to solvent Chloroform Ethanol Toluene Hexane Water Bio Oil Weight transfer to solvent per 1mg Chloroform Ethanol Toluene Hexane Water CryoGTR MBO Chloroform Ethanol Toluene Hexane Water Heat Treated Bio Oil Chloroform Ethanol Toluene Hexane Water : mass increase to values > 100% is indicative of a chemical reaction 2

11 Table 2 Solubility of candidates for asphalt binders derived from recycled resources Sludge from Cellulose (10h of reaction time) Empty weight with Added sample Final Weight transfer Weight transfer to Solvent label and lid weight weight to solvent solvent per 1mg Chloroform Ethanol Toluene Hexane Water Sludge from Cellulose (20h of reaction time) Chloroform Ethanol Toluene Hexane Water Waste glycerol from Emergent Green Energy Inc. (sample 1) Chloroform Ethanol Toluene Hexane Water Waste glycerol from Emergent Green Energy Inc. (sample 2) Chloroform Ethanol Toluene Hexane Water

12 Cryo Rubber Water Toluene Ethanol Chloroform Hexane Bio Oil Water Toluene Ethanol Chloroform Hexane Cryo GTR Water Toluene Ethanol Chloroform Hexane Heat Treated Bio Oil Water Toluene Ethanol Chloroform Hexane Figure 1 Solubility of the asphalt binder candidates derived from recycled materials 4

13 Lessons from Solubility Measurements 1) Cryo Rubber, Bio Oil, CryoGTR MBO, and Heat Treated Bio Oil from Dr. C. Williams, Iowa State University, were too soluble in water and ethanol to be considered long-term stable asphalt binders. Their ethanol solubilities were ranging from 43.6% (Cryo Rubber) to 97% (Bio Oil). 2) Heat Treatment of Bio Oil improved its physical properties. Therefore, other heat treated materials (cellulose sludge from C6-sugar production for bioethanol and waste glycerol from technical biodiesel production) were investigated as well. 3) Sludge from heat treated cellulose (the procedure is described below) appears to be a good candidate for use as asphalt binder, due to its low water and high toluene and hexane solubility. Furthermore, the toluene and hexane solubility of the material increases with prolonged heat treatment, whereas its water solubility decreases. 4) Both investigated waste glycerol samples from Emergent Green Energy Inc. showed good toluene and hexane solubility and low water solubility. The physical properties of waste glycerol with respect to its use as asphalt binder are slightly inferior compared to the cellulose sludge from ethanol production. However, this is untreated material coming right from the biodiesel plant. Sludge from Cellulose Asphalt binders from waste materials from the production of renewable fuels would revolutionize the industry: the potential for replacing fossil fuel based asphalt materials with renewable materials would be substantial. However, plant-derived materials possess a relatively high water-solubility even after chemical derivatization. Therefore, strategies are needed to 5

14 make these materials more hydrophobic. At the same time, their ability to form networks must be enhanced to permit the formation of durable asphalt. We have conducted a systematic study, in which mixtures of waste materials from the production of cellulosic ethanol and from biodiesel production were heated in a pressure reactor (PARR). We were relying on Doehlert methodology (see Figures 2-4). The resulting materials were characterized by GC/MS (low molecular weight content), and TGA (thermogravimetric analysis to determine the amount of residual hydroxyl groups, which cause water-solubility). Again, the ultimate goal was finding suitable candidates for asphalt binders. It is noteworthy that treating cellulose in water at 170 o C in the presence of 5 percent (by weight) of acidic Fe/Fe3O4/silica catalyst for 20h resulted in 52% (by weight) highly hydrophobic (hexane soluble) material. If this conversion was performed at 180 o C, the amount of soluble material is significantly greater. FTIR analysis indicated that the formed polymeric material is virtually free of hydroxyl groups. This is in very good agreement with the paradigm that heat treatment leads to the loss of polar hydroxyl group and better asphalt binders, especially, if C=C double bonds can be retained. The latter then polymerize during the final heating cycle of asphalt prior to its use as pavement material. 6

15 Figure 2 Doehlert Methodology for determining optical process conditions (amount of catalysts, reaction temperature, and reaction time) 1 Figure 3 Fe/Fe3O4-based acidic catalysts featuring a protective silica shell and sulfamic acid groups for acid-catalyzed degradation of cellulose 2 7

16 Figure 4 Solubility of the organic material resulting from cellulose degradation in four organic solvents Thermogravimetric Analysis The TGA experiments were designed to elucidate the temperature range, in which dehydration occurs. Furthermore, the thermal stability of the asphalt binder candidates eas evaluated. It is of great importance that a significant amount of organic matter remains at high temperatures (> 450 o C). Otherwise the materials are oxidized too easily to be viable candidates for asphalt binders. 8

17 Figure 5 Thermogravimetric analysis (mass in mg vs. temperature in oc) of pure cellulose, cellulose sludge (10h of reaction at 170oC (see above)) and cellulose sludge (20h of reaction at 170oC). The heating rate was 5 degrees C per minute under nitrogen atmosphere The organic material (cellulose sludge) obtained from cellulose after 10h of heating at 170 o C retained 16% of macromolecular mass at 450 o C. Furthermore, the thermal stability of the formed polymeric substance was excellent, as discerned from the significant material weight at 1000 o C (9.4% by weight). The organic material (cellulose sludge) obtained from cellulose after 20h of heating at 170 o C retained 22% of macromolecular mass at 450 o C, but only less than 1 percent at 1000 o C. From this data, it is evident that cellulose sludge after 10h of reaction at 170 o C is clearly superior than cellulose sludge after 20h of reaction at 170 o C, although the physical properties of the latter material are advantageous. 9

18 Figure 6 Thermogravimetric analysis (mass in mg vs. temperature in o C) Bio Oil (oil and solid separately), Cryo Rubber, Cryo GTR, and heat treated Bio Oil. The heating rate was 5 degrees C per minute under nitrogen atmosphere It is noteworthy that Cryo Rubber (44 % mass retention at 450 o C, 27% at 1000 o C), heat treated bio oil (58 % mass retention at 450 o C, 26% at 1000 o C), and Cryo GTR (60 % mass retention at 450 o C, 29% at 1000 o C) performed very well. Again, the same trend was discerned: materials, which are more soluble in polar solvents (water/ethanol) perform better during TGA analysis. Therefore, we were able to conclude that this methodology can be used to optimize the required heating conditions of the precursor materials to convert them into asphalt binders. 10

19 Figure 7 Thermogravimetric analysis (mass in mg vs. temperature in o C) of Waste Glycerol from Emergent Green Energy Inc. The heating rate was 5 degrees C per minute under nitrogen atmosphere The last material that was investigated by means of thermogravimetric analysis was Waste Glycerol from Emergent Green Energy Inc. (31 % mass retention at 450 o C, 2% at 1000 o C). It is noteworthy that this sample did not require pre-treatment. This material proved to be not as thermally stable as the materials provided by Dr. Williams, Institute of Transportation, Iowa State University or the cellulose sludge samples from Battelle Institute. However, it could be mixed with other asphalt precursor materials and will be able to act as asphalt binder, because it features great thermal stability in the range of 500 to 750 o C. Further experiments will be required to confirm these findings. 11

20 Summary Sludge from cellulose that was pretreated for the generation of C6-sugars for ethanol production and waste glycerol from Emergent Green Energy Inc. (Minneola, Kansas) are both promising materials for the generation of asphalt binders from waste materials. References 1 Wendel, S. O.; Perera, A. S.; Pfromm, P. H.; Czermak, P.; Bossmann, S. H., Fermentation optimization of Mycobacterium smegmatis using experimental design. Br. J. Appl. Sci. Technol. 2014, 4 (10), , 13, and reference quoted therein. 2 Wang, H.; Wu, X.; Wang, D.; Bossmann, S. H., Acid-functionalized magnetic nanoparticle as catalyst for biodiesel synthesis. Prepr. - Am. Chem. Soc., Div. Energy Fuels 2012, 57 (2), ; Wang, H.; Covarrubias, J.; Prock, H.; Wu, X.; Wang, D.; Bossmann, S. H., Acid- Functionalized Magnetic Nanoparticle as Heterogeneous Catalysts for Biodiesel Synthesis. J. Phys. Chem. C 2015, 119 (46), Temperature ( 0 C) 12