®

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.

New Generation Bio-Binder Formulation

Report # MATC-KSU: 261 Final Report

Stefan H. Bossmann, Ph.D.TaProfessorDepartment of ChemistryKansas State University

Hongwang Wang, Ph.D.Postdoctoral Research Associate

Department of Chemistry

Kansas State University

Sebastian O. Wendel, Ph.D.Asanka S. YapaPalamandadige K. FernandoJose Covarrubias

2016

A Cooperative Research Project sponsored by U.S. Department of Transportation- Office of the AssistantSecretary for Research and Technology

WBS:25-1121-0003-261

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

ii

Technical Report Documentation Page 1. Report No. WBS# 25-1121-0003-261

2. Government Accession No.

3. Recipient's Catalog No.

4. Title and Subtitle New Generation Bio-Binder Formulation

5. Report Date May 2015

6. Performing Organization Code

7. Author(s) Bossmann, S.; Wang, H.; Wendel, S.; Yapa, A.S.; Fernando, P.K.; and J. Covarrubias

8. Performing Organization Report No. WBS# 25-1121-0003-261

9. Performing Organization Name and Address Mid-America Transportation Center 2200 Vine St. PO Box 830851 Lincoln, NE 68583-0851

10. Work Unit No. (TRAIS)

11. Contract or Grant No.

12. Sponsoring Agency Name and Address Research and Innovative Technology Administration University Transportation Centers Program Washington, DC 20590 USA

13. Type of Report and Period Covered July 2013 – November 2015

14. Sponsoring Agency Code MATC TRB RiP No. 35128

15. Supplementary Notes

16. 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 12

22. Price

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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

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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

v

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

vi

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.

vii

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.

1

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 = -0.235), 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.

2

Table 1 Solubility of candidates for asphalt binders derived from recycled resources

Cryo Rubber

Solvent Empty weight with

label and lid

Added sample weight

Final weight

Weight transfer to solvent

Weight transfer to solvent per 1mg

Chloroform 14615.9 50.9 14667.9 -1.1 -0.021 Ethanol 14668.3 50.9 14675.6 43.6 0.856 Toluene 14649.6 50.1 14688.5 11.2 0.223 Hexane 14654.9 50.1 14677.7 27.3 0.544 Water 14647.6 51 14672.8 25.8 0.505

Bio Oil

Chloroform 14756 256.3 14829.3 183 0.714 Ethanol1 14754.2 78.6 14735.9 96.9 1.232 Toluene 14766 135.4 14859.4 42 0.310 Hexane 14731.2 89.6 14783 37.8 0.421 Water 14789.3 46.2 14792.2 43.3 0.937

CryoGTR MBO

Chloroform 14725.2 53.3 14789 -10.5 -0.196 Ethanol 14830 50.7 14830.7 50 0.986 Toluene 14781.3 55 14814.6 21.7 0.394 Hexane 14763.1 50.7 14792.1 21.7 0.428 Water 14825.5 52.6 14856.5 21.6 0.410

Heat Treated Bio Oil

Chloroform 14815.4 47.6 14815.4 47.6 1.000 Ethanol 14768.8 59.2 14776.6 51.4 0.868 Toluene 14776.7 45.2 14811.9 10 0.221 Hexane 14863.3 54.1 14904.2 13.2 0.243 Water 14837.9 49.2 14872 15.1 0.306

1: mass increase to values > 100% is indicative of a chemical reaction

3

Table 2 Solubility of candidates for asphalt binders derived from recycled resources

Sludge from Cellulose (10h of reaction time)

Solvent Empty weight with label and lid

Added sample weight

Final weight

Weight transfer to solvent

Weight transfer to solvent per 1mg

Chloroform 14621.8 50.9 14655.5 16.3 0.322 Ethanol 14643.5 50.8 14685.5 8.78 0.173 Toluene 14649.1 50.2 14671.3 27.9 0.557 Hexane 14636.9 50.0 14656.0 30.9 0.618 Water 14650.5 50.8 14696.2 5.13 0.101

Sludge from Cellulose (20h of reaction time) Chloroform 14738.4 50.2 14766.2 22.3 0.445 Ethanol 14739.7 50.3 14785.5 4.42 0.088 Toluene 14743.5 51.1 14760.4 34.1 0.669 Hexane 14738.2 50.8 14753.3 35.6 0.702 Water 14769.1 52.2 14818.6 2.71 0.052

Waste glycerol from Emergent Green Energy Inc. (sample 1)

Chloroform 14733.0 50.5 14743.5 39.4 0.781 Ethanol 14728.9 50.9 14774.8 4.93 0.097 Toluene 14749.4 50.5 14769.4 30.4 0.602 Hexane 14751.3 50.1 14773.6 27.7 0.554 Water 14741.5 50.2 14787.3 4.36 0.087

Waste glycerol from Emergent Green Energy Inc. (sample 2) Chloroform 14730.5 50.6 14740.4 40.6 0.803 Ethanol 14760.8 50.0 14806.3 4.45 0.089 Toluene 14750.9 51.0 14766.5 30.1 0.591 Hexane 14745.7 50.6 14767.3 28.9 0.573 Water 14746.3 50.5 14792.8 3.98 0.079

4

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

5

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

6

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 170oC 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 180oC, 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.

7

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 cellulose2

8

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 (> 450oC). Otherwise the materials are oxidized too easily to be viable candidates

for asphalt binders.

9

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

170oC retained 16% of macromolecular mass at 450oC. Furthermore, the thermal stability of the

formed polymeric substance was excellent, as discerned from the significant material weight at

1000 oC (9.4% by weight).

The organic material (cellulose sludge) obtained from cellulose after 20h of heating at

170oC retained 22% of macromolecular mass at 450oC, but only less than 1 percent at 1000 oC.

From this data, it is evident that cellulose sludge after 10h of reaction at 170oC is clearly superior

than cellulose sludge after 20h of reaction at 170oC, although the physical properties of the latter

material are advantageous.

10

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

It is noteworthy that Cryo Rubber (44 % mass retention at 450 oC, 27% at 1000 oC), heat

treated bio oil (58 % mass retention at 450 oC, 26% at 1000 oC), and Cryo GTR (60 % mass

retention at 450 oC, 29% at 1000 oC) 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.

11

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

The last material that was investigated by means of thermogravimetric analysis was

Waste Glycerol from Emergent Green Energy Inc. (31 % mass retention at 450 oC, 2% at 1000

oC). 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 750oC. Further experiments will be

required to confirm these findings.

12

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), 1472-1484, 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), 177-178; 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), 26020-26028.

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