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    Volume 81 ASPHALT PAVING TECHNOLOGY | 2012 JOURNAL OF THE ASSOCIATION OF ASPHALT PAVING TECHNOLOGISTS Asphalt Paying Technology 2012—Volume 81 Prado DESech Publications, ne 439 Noth Duke Sect, Lancaster, Pennsylvania 17602 USA Copyrigtn © 2012 All rights reserved Association of Asphalt Paving Teshologias No ar ofthis publication may be reproduced sored in ¢ reteval system, or sansmuted, nn form or by any means, slexroni, mechanical, photocopying. recoding or arise, ‘Sithoat dhe pce writen permission of the Associaton of Asphalt Paving Techoologits ringed in the United State af America woR7Te S432 Main nity unde tie: ‘Aspult Pavieg Technology 2012—Volune #L ISSN No. 0270-2932 Copyrighted material Journals of the Association were printed for the meetings listed below ‘and may be obtained from the Secretary-Treasurer, 6776 Lake Drive, Suite 215, Lino Lakes MN 55014 1074 Witiamburg, Vol 481500 1998 Howton Va. 6? 1973 Phonic, Vol A 2000 1998 Chicago, Vek 8 107? San Anwoin, Volto 3800 199075" Aen, Volume 684, 1982 Kansas, Val.s1| 4000 2000 Reno, VoL 198 Atota, Vo 32 00 2001 Clearwater Vl. 70 1981 Sentade, Vol $3 S00 22 CO Springs Vo. 71 1986 Clearwater soo 2003 Lexiogin, Vol. 72 1988 Willassbure Vol 8? $800 2008 Baton Rouge, Val. 73 1938 Nadine Ved Sk S800 2008 Long Heo, Vol 74 1090 Abaquenae Vol 397 S800 2016 Svannah Vols 1991 Seni Vl joo 22007 Sn Ai, VoL 76 192 Chae, Vol. 61 00 2008 Palin Vo. 77 1993 Avan, Vo wor 2000 Minaepois, V.78 4st Low Vols LOD 2010 serameme, Vol 79 1908 Rtland, Val 68 soo 2011 Tampa, Vot 1966 Raine, Vol 687000 2012 ‘Anat, ol KL 197 Satake Cy. Val. 6@ 7500 Prices to AAPT members for extra copies of the Joumal are $5 less than those listed. “The Association of Asphalt Paving Technologists is not responsible for the statements and opinions advanced in its publications.” ‘Copyright 2012 ‘The Association of Asphalt Paving Technologists ISSN 0270-2932 LS.L. Certified Reprints of Anticles included in Volumes which are out-of-print may be ‘obtained from the AAPT Office. Printed in the United States of America by DesTech, Lancaster, PA, US Copyrighted mater Table of Contents TECHNICAL SESSIONS Laboratory and Field Evaluation of Sustainable Photocatalytic Asphalt Pavements oo dl MARWA HASSAN, LOUAY N. MOHAMMAD, HEATHER DYLLA, SOMAYEH ASADI and SAM COOPER I Renewable Fuel Co-Products—Potential Uses in_ halt... .. 28 (JEFFREY C TREWELLA, RAMON BONAQUIST ond VICENTE SANCHE? Rating Charseterertion of Wars Mis Asphalt and High RAP eee ADRIANA VARGAS-NORDCAECK and DAVID H. TMM Evaluation of Laboratory Coating and Compaction Procedures SANEL SiIZ Se ORAS SAN r r TASH nd HUSSAIN BAHIA Internal Structure Characterization of Asphalt Mixtures for Rutting Performance Using Imaging Characterizing Viscoclastic Properties of ange Mixtures Utilizing Loaded Wheel Tester (LWT)... « of ‘ondition Charact on ra Friction Course Top-Down Cracking Performance...» «. - . 167 Copyrighted material ing of Fatigue Damage Functions for Hot Mix Asphalt and DONALD W. CHRISTENSEN, JR. and RAMON BONAQUIST Recommendations forthe Characterization of RAP Aggregate ing Traditional Testing aad Haibane Yibeetric dat Copyrighted material Laboratory Evaluation of Asphalt Mixtures Containing Dry Added Ground Tire Rubber and a Processing Aid... ...... . 507 ‘GAVLON | BAUMGARDNER. | MICHAEL HEMSLEY, WALTER JORDAN Wf SnGL ISAAC | HOWARD | ‘The Effect of Loose Mix Aging on the Performance of Warm, Mix Asphalt. = Tre +. S41 a MENTS PHLLP. Ki ‘90d KAMYAR C, MAHBOUB | GBS Mix Design: High-Performance and Cost-Effective Asphalt Concretes by Use of Gap-Graded Curves and ‘SBS Modified Bitumens 568 FRANCOIS OLARD Laboratory Evaluation of High Polymes rroduced Nee ‘ond DAVID H. TIMI Relationship between Bond Energy and Total Work of Fracture for Asphalt Binder-Aggregate Systems... ............ 635 JONATHAN HOWSON, EVAD M4 JALLAS LITLE ong EMAD KASSEM ‘Measuring Physico-Chemical Interaction in Mastics Using Gan TRIN a a (CRISTIAN CLOPOTEL. RAUL VELASQUE7 anc HUSSAIN BAHIA Development of a Compact Laboratory Aging Procedure for Aiephalt Dinars on ses cere e sess eseeeys OF IMA YUL ALEXANDER BERNER ond ADAM ZOFKA Delayed Mechanical Response in Modified Asphalt Binders ‘'SYMPOSIUM—TRENDS AND CHALLENGES IN PRODUCTION AND CONSTRUCTION OF HMA. Recent Advances in Production Facilities... 4... ........ 751. BOR FRANK Production and Construction of HMA and WMA: How to Get a Laboratory Mix Design to Work Through the Plant JOHN VICTORY 785 Layer Thickness, Compaction Temperatures, and Achieving Deiiye saeco ts isragna by bation Feat 761 ROBERT L SCHMITT Best Practices for Specifying and Constructing HMA. Longitudinal Joints. . z F we souenene 68 Milling and Paving Operations for Smoothness and Uniformity = i sees 769 Evolution and Direction of Asphalt Specifications and Research Willie Anette DELMAR SALOMON Asphalt Technology in Chile: Leading Research and Practis 75 RODRIGO DELGADILLO, CARLOS WAHR, GABRIEL GARCIA SOGAWARIGOMAIEZ SSS Asphalt Specifications and Research Challenges in Colombia. . . 797 ‘SIMA CARO Advances in Asphalt Research and Specifications in Central ‘America—Costa Rica... os es ee eg awa 40 TUISG-TORA JOSE F AGUIAR: IOWA and JOSE F CORRALES AZOFEFA List of Officers and Life Members. 850 Index of Contributors and Discussors 0 8S CD TABLE OF CONTENTS In addition to the papers listed above, the following items are also included in the CD AAPT List of Members Presentations of Papers Presented at 2012 Annual Meeting, 2012 Annual Meeting Pictures Laboratory and Field Evaluation of Sustainable Photocatalytic Asphalt Pavements Marwa Hassan’, Louay N. Mohammad”, Heather Dylla’, ‘Somayeh Asadi’, and Sam Cooper IIT “Department of Construction Management and Industrial Engineering, Louisiana State University, Baton Rouge, LA 70803. mara tsueda. dyltal @rigers.iswedu. sasadit@lsu.edu, "Department of Chit and Environmental Engineering, Louisiana State University, Baton Rouge, LA 70803. fouayn@ isu ede scoop] 3@lswedu AMSIRACT. Titanium dioxide (T1O;) photocatalytic nanoparticles have the ability wo ap and decompose organic and inorganic air pollaams, making it « promising technology as ovement conting 1 mitigate the harmed effcts of vehicle emlasons. This technology may ‘revolutionize construction and production practices ef hot-mts asphalt by inert a new ‘lass of mistares with superior environmental performance. The objective of hissy was ‘asess the hen of ncomporating THO; is asphalt pavements To achieve this objective, the phovocaalstic effectiveness and durabliy of a watershased spray coating of THO: was ‘cranated in the laboratory. This stay aso present the field performance of the country’s fit cir prising. photocatalytic asphalt pavement, located on the campus of LSU. Laboratory evaluation showed TiO; was efective in removing NO, and SO; pollutants from ‘the ai stream with an efficiency ranging from 31 19 58% for NO, pollaants and 4 to 20% for ‘$0; potas. The maximum NO, and SOs removal efficiency was achieved at an aplication rate of 005 Un’. Adonai, the efcincy of NO, rection is affected by te flow rate of ‘the polluan, relative bumidiy, and UV light intensity. Preliminary ld measurements shose ‘thatthe measured NO concentrations were sigaiicuns reduced right ale the application of the TiO; surface coating on the axphatt pavement. However further field evaluation i= ‘required to determine the durability ofthe surface coating [Kerworns: Sustainable, Tdanian Dias, Photocatalytic, Nitrogen Ovid, HMA. ‘The oral presentation was made by Dr. Hassan. Copyright $ mater HASSAN, MOHAMMAD, DYLLA, ASADI, COOPER A. INTRODUCTION ‘The importance of the national transportation network fo the US economy is indisputable; however, there i a growing recognition that highway eonstruction and ‘maintenance have major environmental impacts (EPA, 1994; Workd Bank, 1996). Road microenvironments contribute 29% of the volatile organic compounds (VOCS), 35% of the nitrogen oxides (NO,), and 58% of the carbon monoxide (CO) ‘emitted in the US (EPA, 1994; Kuhns et al. 2008). These concentrations are often higher in cities where trends of urban development and increase in traffic volumes ‘add to emissions while treet canyon conditions inhibit their dispersion resulting in [high ground level pollutant concentrations. The emissions of harmful air pollutants associated with highway operations often surpass the concentrations from iadustial sources making traffic emissions the primary source of urban air pollution (Baldaut tal. 2008; Thomas et ul, 200K; Chea et al, 2008; Berkowicz et al, 2006). ‘Consequently, many adverse health effects are being linked to areas within 100 m of roads Where pollution is not fully diluted. This affects more than 35 million Americans who live within this proximity limit thus making transportation pollution ‘a major concern (Thomas et al, 2008). Many organic compounds and air pollutants. including nitrogen oxides and sullur oxides, can be decomposed by ultraviolet (UV) radiation but this process is extremely slow, Photocatalytic compounds such as titanium dioxide (TiO) ean accelerate this process by trapping and degrading organic and inorganic particles from the air while removing harmful air pollutants such as NO,, sufur oxides (SO. ), land VOCS in the presence of UV light (sunlight) In addition. their hydrophobic or hydrophilic properties allow hem to self-clean in the presence of rain. The concentrations of water-soluble nitrates and sulfates produced as a result of the [Photocatalytic oxidation were found to reach a level 10 times inferior tothe first pollution level (Kaegi et al, 2008). In spite of these promising findings, this {cchnology has only been applied to conerete inthe laboratory concrete pavements ‘only represent 6% ofthe national road network. About 944% of the road network in the US is surfaced with asphalt, which supports directing futare research towards the use of TIO; im asphalt pavernents. 2. STUDY OBJECTIVES “The objective ofthis study was to determine the benefits of incorporating TiO ia asphalt pavements, The development and validation ofthis new class of sustainable ‘pavements has the potential to mitigate the high levels of pollution dve to traffic. To achieve this objective, photocatalytic effectiveness and durability of a water-based ‘spray coating of THO; was evaluated inthe laboratory and in the field Copyright $ material Laborato Y and Field Evaluation of Sustainable Photocatalytic Asphalt Pavement 3. BACKGROUND Ini interest in environmental photocatalysls hegnn inthe 1970s initiated by Fryishims and Honda's research in photoclectrochemical solar eneray conversion ‘Tarough biomimicry of plant photosyathess, che researchers attempted to replicate the photoinduced redox reactions, by oxidizing water and reducing carbon dioxide, using a semiconlctoriradiated by UV light (Fujishima and Zhang. 2006). Since then, increased interest in environmental photocaalyss was observed, which caused TiO; to be applied to glas, tl. pope. aod povements for self-cleaning materials, ‘water purification, air purification, sterilization, and oil spill remediation. From ‘hese studies, it has been shown that organic and inorganic compounds can he completely decomposed and thatthe TiO, surface has the ability to sel-regenerate (Fjsbima and Zhang, 2006). Therefore rather than absorbing pollants, whieh i ‘vommon te traditional ait porification methods, heterogeneous pholocatalyss can decompose pollutants to nonbazardous waste products with litle energy ‘equiemeats (Zhao and Yang. 2003). Inthe presence of UV light, THO; produces Inydroxyt radicals and superoxides, which are responsible for oxidizing and reducing ‘environmental comamsinantsinclading VOCs and NO, «Fajshina eta. 2000). A proposed mode of oxidation of NO, via hydroxyl radical intermediates in the ‘rescaee of the photocatalyst is described by the following equations No+6H No, +H a NO: + OHNO, +H 2) Based on this heterogeneous photocatalytic oxidation process, NO, are oxidized into water-soluble nitrates; these substances can be washed away by rainfall. AA. Use of THO, in Pavement Applications “The mechanism described in Equations 1 and 2, through which THO, accelerates the decomposition of air pollutants such as NO, from ar in the presence of UV light, js shown in Figure 1. TiO; photocatalytic technologies in pavement applications Ihave been mostly directed towards conerete pavements by applying a photocatalytic ‘concrete overlay, a thin exterior film of suspended THO, nanoparticles in a binding ‘agent (cement), or by sprinkling TiO: nanoparticles on curing coacrete (Dylla etal. 2010, Chen et al, 2007). Researchers. prefer photocatalytic overlays due to their ‘greater durability (Diamant et al., 2008, Beeldens, 2008). Nonetheless, the spray ‘coating application has the advantages of being easy to construct and potentially ‘cheaper to apply to existing pavements. Copyright $ material HASSAN, MOHAMMAD, DYLLA, ASADI, COOPER EL BB l 3 Leo!) som NO, —B Nos tebtiicnn:7 9 © © Ho Ns Argo Pnement “Asphalt Pavement Figure 1 !lusiration ofthe photocatalytic process. Research results by Hassan and co-workers in recent years have measured the impact of common roadway contaminants ineluding motor oil, dit, and de-icing salt ‘on the effectiveness of photocatalytic roadways" ability to remove NO, from the ‘almosphere (Dylla etal, TRB, 2011), Results of the experimental program showed ‘that the theee contaminant types had a strong negative impact on the photocatalytic NO, removal efficiency. The impact of contaminants’ coverage was largely ‘dependent on the soilure type with oil having the largest negative impact. An increase in the flow rate and air relative humidity also resulted in lower NO, efficiencies. Hassan and co-workers evaluated the environmental effectiveness of ‘TiO; coating in photodegrading mixed NO, and NO gases from the atmosphere (Dylla et al, ASCE, 2011). Results of the experimental program determined that Increasing the flow rate and NOYINO, ratio negatively affect the effectiveness of the ‘photocatalytic process. However, the extent of this impact depends on many other factors including flow rate. Few studies attempted to use TiO: in asphalt pavements (Venturini and Bacchi, 200%; Li and Qian, 2009). In Italy, TiO: has been incorporated into asphalt [pavements a8 a thin surface layer that is sprayed on existing pavements (Venturini ‘and Bacchi, 2009). The water-hased emulsion was applied by two different methods, referred to as hot and cold method, distinguished by the spraying of the emulsion ‘during asphalt paving laying operations when the pavement temperature is over 100°C or on existing pavements at ambient temperatures (Venturini and Bacchi, 2009). The study results showed that the reduction efficiencies were highly ‘dependent on the type of TiOs nanoparticles used with NO, reduction efficiency Laboratory and Field Evaluation of Sustainable Photocatalytic Asphalt Pavement ranging from 20 to 57%. Meanwhile, researchers in China mixed TiO; with an asphalt binder at a 2.5% content of the binder weight to an emulsified asphalt pavement (Li and Qian, 2009). Evaluation presented in this study showed that a ‘maximum efficiency in removing nitrogen oxide near 40% was achieved. A more efficient approach may be achieved by concentrating the photocatalytic compound at the pavement surface, 4. METHODOLOGY 4.1. Laboratory Study 4.1.1. Specimen Preparation ‘The application method consisted of applying a water-based surface spray ‘coating of TiO; at three coverage rates (0.026, 0.05, and 0.074 Vim’), Figure 2. The spray coating used was a mixture of TiO; anatase nanoparticles with an average size (of 6 nm suspended in an aqueous liquid at 2% by volume. thin film was spray ‘coated on each sample in layers in a ross hatch formation for each of the three defined coverage rates, Figure 2. Spray-coating of TiO, on HMA samples. ‘The asphalt mix substrates were prepared according to Superpave and LADOTD specifications (Nisa = 8; Nips = 100, Nini = 160 gyrations) and were designed according to AASHTO PP28, “Standard Practice for Superpave Volumetsie Design for HMA” and Section $02 of the 2006 Louisiana Standard Specifications for Roads ‘and Bridges. Asphalt binder graded as PG 64-22 or PG 70-22 was used in the preparation of HMA, Table 1. The optimum asphalt cement content was determined based on volumetric criteria (VIM = 2.5 - 4.5 percent, VMA > 12%, VFA = 68% - HASSAN, MOHAMMAD, DYLLA, ASADI, COOPER 78%) and densification (Gu at Nena « 89, %Gny at Neay S98) requirements. Sillceous limestone aggregates and coarse natural sand were used in the mix design. ‘Table 1. Descriptions of the evaluated samples. Description TIMA prepared with PO 6422 and no TiO: TIMA prepared with PG 70-22 and no TOs ‘surface coating — 01026 Un HMA with PG 70-22 and a TiO, surface coating 0.026 Vint TMA with PG 70-22 and a TiO; surface coating ~ 0.080 Vin" HMA with PG 70-22 and a TiO, surface coating — 0.074 lint 4.1.2, Durability Testing Durability of TiO: surface-coated HMA samples was measured using an ‘accelerated loading test. The Hamburg-type Loaded Wheel Tester (LWT), which ‘employs a sealed dynamic wheel passing back and forth over the specimen, was used in this study co simulate leading and wear of the applied coating. A stee) wheel applied a load of 702 N at a frequency of 56 passes per minule. This test ix ‘considered a torture test that produces significant damage at the surface as the testod slab is submerged in 50°C water, After 20,000 cyeles, the test was stopped and the woen samples were obtained to measure the environmental efficiency after durability testing. Two replicates were tested for each condition considered inthe experimental Program 42. Environmental Efficiency ‘The enviroomental performance of the prepared samples was quantified in the laboratory by measuring the concentrations of NO, NOs, NO,, ani SOs, The test setup used was modified from the Japanese standard (IS TR Z 0018) to ‘accommodate larger samples (JIS, 2004). This setup consists of a pollutant source (gas cylinder of NO}, zero air source, adjustable valves, humidifier, calibrator, Photoreactor, and chemiumiscent NO, and SO, analyzer as shown in Figure 3 Copyright $ material Laboratory and Field Evaluation of Sustainable Photocatalytic Asphalt Pavement Figure 3. Experimental setup flow diagram. ‘The calibrator, requiring & pollutant and zero air source, controls inlet flow and NO, SO; concentrations introduced to the sample through the photoreactor. Before centering the photoreactor, the inlet et stream can continue through the humidifier oF ‘bypass the humidifier to simulate various humidity levels, A tee-connection before ‘the photoreacior is connected to the NO, analyzer to verify the inlet NO, ‘concentrations. AS a result, the jet stream enters the photoreactor flowing over the ‘sample at a controlled humidity, flow, and NO, concentration, The photoreactor ‘maintains this controled environment for the sample. All tests were conducted at ‘oom temperature of 24°C 4/- 2°C. UV lights are above the photoreactor to simulate [UY lighting forthe photocatalytic reaction to oceur. Finally, the outlet jet stream of the photoreactor is connected to the NO, and SO; analyzers to measure any changes in pollutant concentration after being exposed to the sample. HASSAN, MOHAMMAD, DYLLA, ASADI, COOPER 4.3, Field Study To date, field evaluation of photocatalytic pavement technology has been Timited. Massan and co-workers lak! the country’s first air-purifying photocatalytic asphalt and concrete pavements on December 20, 2010. The test area is a pavement site located on LSU campus, soe Figure 4. A computerized distributor truck was used in the application of TiO; water-based solution. Mounted on the back of the truck, a spray bar fitted with nozzles distributed TiO, water-based solution at the specified application rate. Applicaton rate was adjusted by altering the truck speed and nozzle type and size. Figure 4. Field application of photocatalytic pavement coating ‘On-site measurements were conducted to collect air traffic emissions data on the Photocatalytic section as well as from a nearby untreated section, Trafic count. weather parameters, a well as NO, NO: and NO, concentrations at the pavement level were continuously monitored and recorded using a Davis 6152 Wireless Vantage Pro weather station and a Thermo NO, analyzer. The equipment used for monitoring is housed in a movable air-conditioned trailer such thatthe trailer ean be moved between the couted and uncoated areas. Data collected from the field sites were used {0 identify the range of various NO, concentrations and operating and ‘environmental parameters specific 10 the field sites. The data were supplemented with measurements from a nearby Department of Environmental Quality (DEQ) air ‘monitoring station as well as historieal TMY-2 weather data files. The LSU DEQ station provides ambient air pollution hourly averaged concentrations for NO,, SO; ‘and ozone, Laboratory and Field Evaluation of Sustainable Photocatalytic Axphalt Pavement 5. RESULT AND ANALYSIS S.J. Laboratory Experiment 5.1.1. NO, Reduction Efficiency Laboratory samples were tested using a flow rate of 1.5 Vimin and a luminosity of 2 mWécr*. Figure 5 illustrates the variation of NO, concentration during the course ‘of the environmental experiment for the asphl specimen treated with « TiO; ‘surface spray coat with a coverage rate of 0.050 Vin". The UV light was turned on 1.5 hours after the start of the experiment in order to ensure equilibrium condition ‘The inlet concentration reached equilibrium at 430 ppb before the light was turned ‘60, Afler the light was turned on, a fast drop of NO concentration in the outlet air ‘stream was exhibited and NO; was created from the NO oxidation. Daring the ‘photocatalytic experiment, the NO, concentration slightly increased. Alter 5.5 hours ‘of testing, the light and gas supply were turned off allowing for any desorption to ‘occur. For the test condition shown in Figure S, the use of TiO photocatalyst ‘coating had an NO removal efficiency of $3% and the overall NO, reduction was 56%, ime ae “eer oe Po Figure § Variation of NO, concentration during the environmental experiment (TiO: applied at a 0.050 Vint coverage). "The results forall of test conditions are shown in Table 2. Table 2also presents the measured NO efficiency forthe asphalt sample that was not treated with TiO; [As shown in this figure, the efficieney of the sample without TiO; was negligible, HASSAN, MOHAMMAD, DYLLA, ASADI, COOPER validating the efficiency of the photocatalytic compound in removing patt of the NO, pollutants in the sir stream when used as a spray coating. By comparing the effect of the TiO, coverage rate, it appears that the improvement of NO, reduction is ‘not linea. In Tact, the maximum environmental performance was achieved at 0.050 Ym? coverage rate. The increase in TiO, application rate beyond an optimum ‘coverage ate may block nanoparticles’ access to light and contaminants, and ‘therefore, decrease NO, removal efficiency. ‘Table 2. Average NO, reduction and NO reduction for ‘THO, wsed asa thin surface coating. ‘Control PG (64-23) ‘Control PG (70-23) PG (64-22) 0.026 Un PG (64-33) 0.080 Vin™ PG (64-23) 0074 Un PG (70-22) 0.026 Vin® PG (70-23) 0.050 Vn PG (70-23) 0.474 Vine™ 52. Durability of TiO; Surface Coating Durability of TiO, surface-cooted HMA samples was determined using an accelerated loading test by measuring NO, removal effickency before and after darabilty testing. Figure 6 presents the average NO, removal efficiencies for the ‘iginal and worn samples (Joaded-wheel test samples) treated with the THO, surface ‘spray coating. As shown in this figure, the wearing of the samples resulted in a significant decrease in the ccaling NO, removal efficiency. An average 685% ‘decrease in NO, reduction efficiency was observed after LWT testing. While there ‘was a significant decrease in NO, reduction efficiency. it was noted that the HMA specimens were significantly distorted after LWT testing. It is not expected that ‘such excessive distortion will eceur inthe field. Nonetheless, these results indicate that the durability of the THO, surface coating should be closely monitored in field applications ofthis technology. 0 Copyright $ material Laboratory and Field Evaluation of Sustainable Photocatalytic Asphalt Pavement Before LWT After LWT TWH SC-64L) SC-64L2 §C-64L3 SC-70L1 SC-70L2 $C-70L3 ‘Sample 1D 6.NO, removal efficiency before and after loading in the LWT. NOx Reduction Efficiency s 5.21. Effects of Operating Conditions Figure 7 presents the effects of air relative humidity on NO, reduction efficiency for the HMA sample treated with TiO; surface coating (Level 2 ~ 0.05 Vn). As shoven in this figure, humidity had a negative impact on NO, reduction efficiency as the increase in relative humidity resulted in a decrease in NO, removal efficiency. It js possible that at high relative humidity, the water molecules interfere sith NO, ‘contact 10 the TiO, active sites on the surface. Figure 8 presents the effects of the pollutants’ flow rate on NO, removal efficiency for the HMA sample treated with ‘TiO, surface coating (Level 2 ~ 0.050 Vi). AS shown in this figure, the increase in flow rate bad a significant impact on NO, reduction efficiencies. With faster Flow ‘ates, there is less contact time forthe photocatalytic reaction to oceur, which results in lower reduction efficiencies. HASSAN, MOHAMMAD, DYLLA, ASADI, COOPER, 1s 20 30 Potato Rat min Figure 8. Effects of pollutants’ flow rate on NO, reduction efficiency. Figure 9 presents the effects of UV light intensity on NO, removal efficiency. ‘While the presence of UV light is necessary 10 initiate the photocatalytic reaction, ‘the required light intensity is not known, Resulls presented in Figure 9 show a direct correlation between light intensity and NO, removal efficiency with greater pollutant ahatement at higher UV light intensity. Copyrighted material Laboratory and Evaluation of Sustainable Photocatalytic Asphalt Pavement 2 2 os [UY Laghetmtemsty (Wem?) Figure 9. fects of UV light intensity on NO, reduction efficiency. $2.2. $0; Reduction Figure 10 illustrates the variation of SO; concentration during the course of the ‘environmental experiment fo the asphalt specimen treated with a TiO surface spray coat witha coverage rate of 0.080 Un’. The UV light was tuned on 28 hours after the start of the experiment in order to ensure an equilibrium condition. The inlet concentration reached equilibrium at 175 ppb before the light was turned on. After the light was turned on, a deop of SO; concentration in the outlet aie stream was exhibited. After 5.0 hours of testing, the light and gas supply were tured off allowing for any desorption to occu. For the test condition shown in Figure 10 the ‘use of TiO; photocatalyst coating had an SO; removal efficiency of 23%. ‘The results for all of the test conditions are shown in Table 3. While SOs reduction efficiency was inferior to the ones observed for NO,, the removal of SO: 4s crucial as it 8 a major air pollutant and has significant impacts upow human ‘health. Similar to NO, reduction elfigiency, the maximum environmental performance was achieved at 0.050 Vim? coverage rate with an average SOs reduction efficiency of 19.8%. Copyrighted material HASSAN, MOHAMMAD, DYLLA, ASADI, COOPER ‘Arerage Rachel Ope Figure 10. Variation of SOs concentration daring the environmental experiment (TiO: applied at a 0.050 Une coverage) ‘Table 3. Average $0: reduction for TiO, used as a thin surface coating ‘SO; Reduction, % ‘Control PG (64-22) ‘Control PG (70-22) PG (64-22) 0.026 Vin PG (64-22) 0.05 Ve PG (64-22) 0.074 Vm PG (70-22) 0.026 Vim* [PG (70-22) 0.05 Vm? PG (70-22) 0.074 Vin 5.3, Field Experiments Measurements of pollution reducts 36% Sa% 10% 19.8% in the Field presented a challenge due to & large number of influencing parameters, time, and costs. In the described Field ‘experiment, NO concentration was measured at the pavement level by placing a perforated pipe atthe surface in the middle of the lane. Preliminary measurements of WW Laboratory and Field Evaluation of Sustainable Photocatalytic Asphalt Pavement NO concentrations in the field showed high variability due to the influence of ‘numerous factors including wind speed, vehicle type, humidity, and temperature. ‘To determine NO reduction efficiency in the field, ten days of data were ‘compared just before and alter TiO; applications. Figure 11 compares the measured nitrogen exide (NO) data collected just before and just after application of TiO: for ‘several days during the winter season. As shown in this figure, the measured NO ‘concentrations were significantly reduced right after the application of the TiO: surface coating on the asphalt pavement. This difference shows the important role of ‘TiO; in reducing nitrogen oxide inthe environment. ote) ou sRsUsess Figure 11..NO concentration reduction efficiency inthe ied Due to the limitations in equipment, NO measurements were not conducted ‘concurrently on the treated and untreated sections after TiO; application. To address Jimitation and to quantity the level of NO concentrations collected under different environmental and traffic conditions, nonlinear regression models were ‘developed for predicting NO concentrations before and after TiO; application based fon the field data The regression models were then used 10 compare NO concentrations with and without TiO, under similar operating conditions. The ‘developed regression models relate the measured NO concentration linearly to the ‘operating faclos as follows: NO = /(T,H,V,Tout,s) BI NO pee = 0.96¥T40.229H-1.33" Toy -10.5*V40.02"S NO ur = 0.31 #0,069H-0.75*V-0.1" T.qct0.0003*S, 1s HASSAN, MOHAMMAD, DYLLA, ASADI, COOPER where, [NO = NO concentration atthe pavement level in ppb; ‘T= number of vehiele per hour: H= relative humidity: V = wind speed: ‘Teas outside temperature; and 'S solar radiation Formulation of the models was divided into (wo steps: model development and ‘mode! validation through independent measurements. Statistical goodness of ft was ‘also assessed through the coefficient of determination (R") as presented in Table 4 ‘The developed models are cely valid in the input ranges shown in Table 4, Based on ‘the measured data, i¢ Was found that NO reduction due to photocatalytic pavement should not be expected ata relative humidity greater than 88%. Table 4, Descriptive statistic ofthe developed models. Range of variation Parameters ——— Tow Level Viigh Level Number of vehiele per our Es Humidity (%) 88 ‘Wind speed (m/s) 27 ‘Outside temperature (°C) 20 Solar Radiation (Whm") 658 Coefficient of Determination (R") Untreated = 0.79 | Treated = 0.67 Figures 12 and 13 compare the measured und predicted NO before and after TiO: application, respectively. As shown in these figures, the models. successfully respond to the peak increases in NO concentration, which are usually due to the passage of a large vebicle (e.g, bus, truck). However, the model response to regular ‘passenger vehicles was not as timely as it was observed in the measurements It 8 noted that environmental variability in NO measurements in the field is around 10 ppb. 6 Copyright $ material Laboratory and Field Evaluation of Sustainable Photocatalytic Asphalt Pavement Figure 12. Nitrogen oxide (NO}—before application. NO Feit NO wee ssseeess HARASS RRS SH eRe TEE Mensoreneat 19) Figure 13. Nurogen oxide (NO}—after application. Based on the developed models, Figure 14 shows the NO reduction efficiency ‘due to the photocatalytic coating at different levels of wind speed and solar ‘radiation. AS shown in this figure, the maximum NO reduction efficiency was ‘determined at high solar radiation and low wind speed. At high solar radiation (1000 Wim’), the reduction of NO is approximately 83%. In addition, by changing the wind speed from 0 mvs to 3 m/s NO reduction drops from 62 to 15%. To provide ‘additional insight in the measurements and to assess the durability of the coating, NO, concentrations will be continuously monitored at the test site at regular time {intervals to validate these trends. 0 HASSAN, MOHAMMAD, DYLLA, ASADI, COOPER a. Wind speed effect bs, Solar radiation effect Figure 14. Nitrogen oxide (NO) reduction efficiency. 6. SUMMARY AND CONCLUSIONS ‘The use of titanium dioxide coating for pavements has received considerable attention in recent years to improve air quality near large metropolitan areas However, the proper method of applying titanium dioxide to asphalt pavements is Sill unclear. The objective of this study was to assess the benefits of incorporating nium dioxide ia asphalt pavements. To achieve this objective, the photocatalytic effectiveness and durability of a water-based spray coating of TiO. was evaluated in the laboratory as well asin the field. The test area isa pavement site located on the LSU campus. Based on the results of this study, the following conclusions may be drawn: As part of a surface spray coating, THO: was effective in removing NO, Pollitt fom the air steam with an efficiency ranging from 31 wo 33% in the laboratory, The maximum NO, removal efiiency was achieved at ‘coverage rate of 0,05 Vm", However, durability of the surface spray coating requires further evalsation and monitoring in fel applications. ‘The increase inflow rate and relative humidity negatively affected the NOx reduction eficieney. However, the increas in UV light intensity improved the NO, removal efficiency ofthe surface coating. TiO: was etfoctve in removing SOs pollutants from the sir stream. The maxim environmental performance was achieved at 0.05 Vi? coverage rate with an SO, reduction efficiency of 19.8% Preliminary field measurements show that the measured NO concentrations were significantly reduced right aftr the application ofthe THO: surface cating on the {phat pavement, To evaluate the daability and long-term effectiveness of the technology. NO, concentrations wil be coninaously monitored en the test it regular ime intervals vo validate these trends. Laborato Y and Field Evaluation of Sustainable Photocatalytic Asphalt Pavement 7. ACKNOWLEDGEMENT. ‘This work was funded through a grant from the Gulf Coast Research Center for Evacuation and Transportation Resiliency. The authors would like 1o acknowledge PURETI for donating the materials needed for the construction of the fied study and the support of Louisiana Transportation Research Center (LLTRC) for granting access tw their laboratory. ‘8 REFERENCES Bald, R.. Thoma, E., Hays, M., Shores, R. Key, J, Gilet, B., Kissbroagh, S, lsakow, 'V., Long. T. Snow. R. Kilystoy, A, Weinscin, J Chen, F Sella, R, Olsoa, D., Gilmour 1. Cho. 8. Watkins. N.. Rowley. P.. and Bang. J. Trae and meteorological impacts on ear-toad ae quali: Sumanary of methods and res trom the Raleigh near road sly. Air & Waste Management Association, No 58, 2008. 865-878. Beeldens, A. "Air purication by paverent Blocks: Final results ofthe research atthe BRC” Transport Research Arena Europe. 2008, Lhjana Beskowicz, R., Winther, M., aad Ketzl, M. Tete pllstion modelling and emission data. Pncionmental Modeling & Softward, Vo. 21,2006, A446, ‘Chen, DAM. Li, K. and Yuan. R “Photocatalytic coating on road pavementvstrocures for ‘NOx abatement." Houston Advanced Research Cemter, 2007, I=L ‘Chen, Hy A. Nownco, and M. Bel, Clasification of rood traffic and roadside potion ‘conceuratons for assessment of personal exposure. Environmental Meselling & ‘Software, Va 23, 2008, 282-287, Diamar, M. V.; Ormellex, Mand Peder, M.P. "Characterization of photocatalytic and uper hydrophilic propenies of moras comtsining titanium diotide.” Cement and Concrete Research, 2008, Nol. 38, 1349-1383. Dylla, H, Hasan, M.M., Mohammad L and Rupoow T. Elects of Roadway Contaminants ‘om Titanium Dioxide Photodepradation of NOX. Teunspornation Research. Record: Journal ofthe Transportation Research Board, 2240, 2011, Washington, D.C, 22-29. Dalla, Hh, Hassan, M. M. Schmit, M. Rupnow TT, and. Mohammad b.. Laborstory Investigation of the Effect of Mixed Nitrogen Dioxide (NO2) and Nitrogea Oxide (NO} ‘Gases on Titanium Dioxide Photocaalic Efficiency” ASCE: Journal of Material in Givi Engineering, Vo 23, Fem 7, 2011, 1087-1003, Dalla, FL, Hassan, MLM. Mohammad, L. and Rupoow. T, Evaluation ofthe Environmental Eftectiveness of Titanium Dioxide Photocaalyst Coating for Concrete Pavements. Transporation Research Record: Journal ofthe Transportation Research Bown, 2164, 2010, Washington. D.C. 46-51 Foujshina, A, and Zhang, X. “Titan dioxide photoeatalysis:preseat station and fue approaches.” C RChimie 2006, VoL. 9, 750-760, Fujshina, A. Rao, T.N. and Tryk. DLA. "Titaniam Diokide Photocitalyss." Journal of| Photochemisty aed Photobiology. C: Photchemisry Reviews, 2000, Val. 1, 12 1» Copyright $ material HASSAN, MOHAMMAD, DYLLA, ASADI, COOPER Japanese Fadil Standard (JTS). Fine ceramics (advanced ceramies, advanced technical ‘ceramics)~ Test method for air purication performance of photocatalytic material Pat 1: Removal of mite oxide, ISR 1701-1, 2004, 1-9. Xaogi,R., Ulrich, A, inne, B.. Vonhank. R. Wichser, A. Zuleeg. 8, Sime. H. Brunner. 'S, Vonmont, H., Burkhart, M, Boller, M, Synthctic TSO; Nanoparticle Emission fom Entetioe Facade inte the Aquatic Enviroameat. Environmental Pollution, 2008, 156, 202, Kuhas, H.D., Mazzoleai C, Moosmaler H, Nikolic, D Keislar, RE, Buber, PW. Li.Z., nyemezian, V., and Wats, JG. Remote sensing of PM, NO, CO, HC emission factors for on-road gasoline and diesel engine vehicles in Las Vegas NV. Science ofthe Total Ensivonment, Vol. 322, 2004, 125-137. Li Land Qian, C. A Lab Study of Photo-Catalyic Oxidation and Removal of Nitrogen ‘Onides in Vehicular Emissions and is Fieldwork on Nanjing No. 3 Bridge of Yangtze River. Technical Noe fteretional Journal of Pavement Research aad Technologs. Vel 2,No. 5, 2008, 218-222. ‘Thomss, E.D., RC. Shores, V. Isshov, and RW, Baldaut, Characterization of wearroad pollutant gradients using path inegraied optical remote sensing. Air & waste ‘Management Assocation, Nol. $8, 2008, 879-900 US. Environmental Prowetion Agency (EPA). Evaluation of Ecological Impacts from Highway Development, EPA 00:8-54-006, Washington, D.C, 194. Venti, Land Bacehi, M. Research, Design and Development ofa Photocatalytic Asphalt Pavement. Proceedings of 2” Iniernatimal Conference an Ensironmentally Friendly Roads ENVIROAD 2009, Warsi, Poland, 29. ‘World Bank. The Impact of Environmental Assessment: Second Eavioamestal Asscsament Review of Projects, Washiagtoa, DC: World Bank, Esvironmens Department, 1996 ‘too, J. aad Yang. X. “Photocatalytic oxidation of indoor air purification: » Meraure review" Building and Environment, 2003, ol. 38.655-454, 9. DISCUSSION DR. ERVIN DUKATZ: | have two guestions. The first of which is about your Feld study. How critical was the preparation of the surface before spraying on the iam dioxide solution? MS, HEATHER DYLLA: You do want to prepare the surface, The manufacturer ‘of titanium dioxide spray coat said to brush itor spray it with air to get off all the debris. If you have any debris on it t's not going to stick to your surface and the ‘spray will just go off with the debris. So that was taken into account. If there's anything else, Dr. Hassan, do you want to add? The spray coat requires certain ‘weather conditions, so we got delayed and I wasn’t actually there DR. DUKATZ: Okay. So, did you put it down in a two-cost process, frst spraying «prime coat forthe estalyst, and then spraying the actual catalyst solution on top of that? Copyright $ material Y and Field Evaluation of Sustainable Photocatalytic Asphalt Pavement DR. MARWA HASSAN: I just want to highlight what Heather said. The most ‘important thing is just getting ei of the debs, like dust particles, and air blowing ‘the pavement was all that was needed. The second part that she's talking about is worrying about meteorological conditions. This was a job that was done by stadents a LSU, as you can see from the distributor truck. Once we actually used something ‘Similar to a tack coat application, then that's not going wo be a problem. What you need is you have the nozzles that are capable of spraying the manoparticles and distributing them, ‘The distance of the applicator from the surface of the pavement ‘cannot exceed 3 in. so that the wind does not blow it away, because it's very light land you're going to lose very expensive material if that happens. As far as this application method is concerned. yes it was applied in two coats. a prime coat and a top coat, The prime coat is aot photocatalytic in nature. It actually acts as 3 foundation to improve the photocatalytic efficiency of the actual coat. "This is stl new, but we're working with the manufacturer to develop a single coat application where you would actually have to go through the pavement one time, there is no primer needed, and it has a higher honding strength, but that's still on the research, DR. DUKATZ: Thank you very much, My second question is ubout the second [art of your study. Are you looking at freeze-thaw effects? MS, HEATHER DYLLA: Freeze-thaw effects? No, but that’s a good thing to look a. I'm focused more on the other environmental parameters. MR. GALE PAGE: Can [ answer? DR. HASSAN: And actually Heather should have said that because her PRD dissertation is going (o quantify the reaction rate taking place under ‘conditions and although we're sot getting to freeze-thaw. but she is va temperature. We are trying to modify the setup to reach to somewhere around 0 to 10°C to see how we do with that MS. HEATHER DYLLA: Thank you. MR. PAGE: find it interesting that in your UV conditioning of just the binder with ‘and without ttaniur» dioxide thatthe neat binder showed no difference in aging, oF somehow the UV exposure had no effect on the aging ofthe binder. 1 just find that very intresting. MS, DYLLA: Sodid we. MR. PAGE: The other question I've got is regarding the pollutants that you intend to remove: I'm assuming the pollutants are coming from the cars going over the pavement, rather than the axphalt itself. It might be something you might add to the [paper so that it isn't misinterpreted that we're tying to remove pollutants that are somehow coming from the asphalt pavement itself Copyright $ material HASSAN, MOHAMMAD, DYLLA, ASADI, COOPER DR. HASSAN: The aging part, there is an answer to it. When we quantify the ‘aging part, we were having the same suspicion. That's what stared the whole idea, ‘nd that's the part of research that was funded by NSF. No, {just want to say that ‘agree with you although the reality did not do it, we need to do more research in terms of drawing a master curve because there must be something taking place, It's just that the Supespave meteorological testing did not get it. just want to say that this conclusion necds further study before we can say that there is sothing taking place at all DR. JOHN D'ANGELO: Very interesting presentation. One question and a ‘comment. When you did your field evaluation and looked at the aging rates and ‘then also at durability, you didn’t show it here. did you look at things like whee! path and outside the wheel path? Because that's going to be the key issue there, as ‘wear takes place it will take place more in the whee! path, MS, DYLLA: We sprayed over the whole area, and we do have some studies of the nitrates being collected, which showed Jess nitrates in the wheel path than on the ‘curb. I believe that was forthe conerete site and not the asphalt site in particular But that is one area that we were investigating, and I think [missed the second part ‘1 your question. DR. D'ANGELO: | haven't gone to the second part yet. The question is, did you just do the evaluation inthe whee! path then? MS. DYLLA: It was actually in the center. DR. D'ANGELO: So non-shee! path evaluation? MS, DYLLA: Yes, because what we wanted to do was determine the exhaust ‘emissions coming from the vehicles in contact with the roadway. The problem is ‘sometimes you have the exhaust of the left side and sometimes itis on the other side ‘of the vehicle. So to deal with thx we put the pipe in the center. DR. D'ANGELO: Then the other comment is going back to the UV. T would be very careful stating that there was no UV aging because if you go into the literature and. actually look, there is extremely well documented data that UV does age asphalt. Now it usually happens just at the very surface, but it's extensively been ‘documented so it might have been something in the way’ you did testing, something. you missed. But if you go around saying that, st could cause problems with your ‘ther well documented good work, so be careful with that one. MS, DYLLA: Thank you. MR. DALE DECKER: The question I have, I'm intrigued really with kind of different idea, One of the big issues for contractors is SO andl NO, emissions from the stack. Has anybody done any work using this same kind of technology? 1 2 Copyright $ material Laborato Y and Field Evaluation of Sustainable Photocatalytic Asphalt Pavement realize the humidity issue you ruse, but if there was some technique that could spray 4 product like this into a stack (o maybe absorb some the NO, or $0, that ould be & Inuge opportunity or the contracting community, and I just wondered if anybody has fooked at that at all. [think t could be very intriguing. By the way, reat paper. MS, DYLLA: Thanks. From what I found in literature review, there are a Jot of ‘chemical engineers that looked at actual filters that they could put in. 1 don’t know it was at high emission stack plant versus more of a vehicle exhaust, which is ‘smaller scale. But the biggest issue is to get sunlight or some type of source of ‘energy that’s UV. A stack is going to be a much higher level of concentrations, but it's definitely doable for investigation, [think some people have. Copyright $ material Copyrighted material Renewable Fuel Co-Products—Potential Uses in Asphalt Jeffrey C, Trewella, PhD*, Ramon Bonaquist, PhD, PE**, and Vicente Sanchez, MSc, MOT *** *PetroTech Consultants, LLC Manna, XJ, 08051 Jeff46@ gmail.com st tdvanced Asphalt Technologies, LLC Sterling, VA 20166 ‘aatt@erols.com **9KOR, Ine. Pasadena, TX 77507 vicente sancher@kvor.com ABSTAACT. The prodiction of renewable liquid trensportation fics & growing. rapidly orricularty the Uned States and Europe. This paper exananes the potential for wing co- ‘products from ths rapidly growing mamafcturng hase as blending components i aspalt Several blonds of biofuel corproducts m & penny grade axphalt binder were prepared and performance grading properties were measured. Asphalt concrete misores using the various ‘lends nd. somewhat motstare sensive aggregate were teste in accordnce with AASHTO TSS to evaluate resistance to moisture damage. Initial laboratory findings incate shat ome of these materials may Be usfl ax Binder extends, hang minim! impacto the performance grade while imparting ated Benefits. Kevworns: big! asphalt inde, performance graced cells. aniestipging. ‘renewable, Blomass Fld Catasse Crucker “The oral presentation was made by Dr. Trewella 25 ‘TREWELLA, BONAQUIST, SANCHEZ 1. INTRODUCTION In response to environmental, economic, and national security concerns, governments throughout the world have mandated the use of various types of renewable fuels. In Section 2 of this paper, we provide an overview of the United ‘States market, fypes of renewable fuels, manufacturing technologies, co-produets ‘and potential co-product use Section 3 examines the use of several potential ‘materials as extenders in paving grade asphalt binder. Here we describe the results ‘of laboratory testing of several samples in comparison 40 a premium nest asphalt binder. In Section 4 we postulate other co-product modifications and asphalt applications for future evaluation. 2. US. RENEWABLE FUEL MARKET 2.1. Overview ‘The liquid transportation fuels market is the largest market in the world, teptesenting over $2 willion in revenues on a global basis. Key products are ‘gasoline, diese fuel, jet fuel and fuel oil for railroad and marine applications. Each ‘of these finished products is produced by blending together a vanety of blendstocks ‘produced in refineries. These blends are then supplemented with a variety of additives designed to overcome deficiencies (e.g, antioxidants) or impart added benefits e.g, detergency). In ths way, the fuel manufacturing procestes are not ‘like the production of asphalt binder, where various bitumen streams are blended ‘and additized (eg. anti-stipping additive, ubricant), 1m the US, the market for renewable fuels is stimulated by the Renewable Fuel ‘Standards, REST and RFS2 (US EPA, 2009) Combined, these standards correspond to a US market of over $100 billion. Key products are gasoline and diesel fuel ‘endstocks that are denved from nonpetrokum, renewable sources. Table 1 ‘compares the key characterises for each RES2 category of renewable fuels. ‘As Table 1 illustrates, RES2 considers four categories of renewable fuels, Renewable Fue, Advanced Biofuels, Biomass Based Diese, and Cellulosic. tn each of these categories, during the manufacturing process to produce the renewable ful 1a least one product sao co-produced. In most eases the principal product thats co-produced i either alow molecuae weight (MW) gas (CO:) ot igi (glycerol) ‘After the hexane extraction of crop ol, the biomass lef over is solid meal that ‘contains ntrcals. This i normally sold as ate ee. Copyrighte ad mater ‘soy 801920 suyose youoRRaAUND IAL sORZAMONd [eH OFGH|OS STOOAANHO soyeapqoga SemuteyO09 Wox}ae4} Wy JEON BMV ey wan OLE 7} seucq | — won stsjoucg | AEN Taiaig | Se sinsowg | RS iso | arose saeding ompiquy: jourmr |, asses | 2801519 sisijous Lane ed ee Renewable Fuel Co-Produets— Potential Uses im Asphalt “sponf gmones o sounsarsomp ey LAIEL {Psy uoneyods ese pay 29 we yt s20j9q papentdn 9q ASN | ‘140}08uoqseooypy WHE Bie st pu HONO 94pg < sHHHOD SAIOK YO SATOH TREWELLA, BONAQUIST, SANCHEZ Interestingly, there are two technologies within the Cellulosic category that produce high MW co-produets that ean be considered for use in asphalt applications. ‘These are shown inthe last (wo columns of Table I. Asphalt laboratory test results ‘on these materials and their derivatives will be presented in later sections of this paper. ‘Table 2 compares the size of the US. renewable fuel markets. For 2022, RFS? ‘has mandated 36 billion gallons across the four categories ‘The US Energy Information Agency (ELA) has recently forecast that 25,700 ‘million gallons of capacity will be im place within the US by 2022 Most of the ulunce will likely be imported fom Canada (BicDiesel) und South America (Advanced, sogareane ethanol) ‘The last two columns of Table 2 assume a 10% production of co-product. Based ‘on ths assumption, al current reformulated fuel forecasts there could be 68 million tons of material available to the US asphalt industry by 2022 “The armed services are also driving demand The Honorable Ray Mabus, ‘Secretary of the Navy has proclaimed. “Ewergy reform and the new energy economy «are not just talking points. 11's nota political game. it means the tives of onr troops it means making our military better fighers. It means making our country more “independent.” By 2020, half of the Navy's energy consumption vill come from alternative sources (Navy Energy. 2010) (On March 21, the Commandant ofthe Marine Corps (CMC) announced a “Marine Comps strategy to change the way we use energy’ ~ with the intent to increase ‘comibal effectiveness and reduce our need for logistics support ashore (U.S. Marine ‘Comps, 2010). As part oF a 3-prong sategy the CMC stated; “we must mervase our suse of renewable energy though smnovation and adaptation 2.2. Cellulosic Technology Economies Recently researchers at lowa State University, ConocoPhillips, and the National Renewable Energy Laboratory (NREL) estimated the Net Present Value (@10%), expressed in dollars per gallon of gasoline equivalent (S/GGE), using the same assumptions for each of six cellulosic conversion technologies (Anex et.al, 2010), Table 3 summarizes their findings AAs Table 3 illustrates, both of the pyrolysis cases considered have the lowest ‘capital and S/GGE, ‘Thas analysis suggests thot some form of pyrolysis isthe most Likely technology to be commercialized to meet RFS2 mandates In addition, ‘without govemment subsidies, occording to this analysis, both pyrolysis cases are competitive with gasoline at $3 per gallon at the refinery gate (before taxes and ‘distribution cost Copyright $ material Renewable Fuel CorProduets Potential Uses in Asphalt wo TOT mar ee TRL ccoe 89 o08't SISOROTD o 0 PEDO 0 0 Poouespy 0 0 ‘Wo0s1 RENE SO BOAT SRD COTA | SSO WON | SIOUPD WOH | sae ery “01 @ meudsy jenared | “s601 DwaRsy reoMayog | Bion yorum vis | “Teo MESEPUNR -youdso un asn yoncsod Suen stonpoad-o9 janf 1pm?) ZANE, Copyrightes material TREWELLA, BONAQUIST, SANCHEZ Table 3, Total capital investment and product value for ‘cellulosic renewable fuels ps Capital] Product Investment, | Value, sum | sick Biochemical | Dilute Ach hase a Dilute Aci igh sods) | 90 | 5.0 ci | High Temperature | 430 Gasticaton [Tow Temperature 200 [820 Pyrotyris | Hydrogen production 230 300 Hydrogen purchase 00 [00 2.2. Cellutasie Product Testing in Asphalt ‘As noted in Tables 1 and 2, cellulosic technologies are abe to produce high MW products for potential use in asphalt products, At least two companies have technologies and are moving forward with evaluating products im asphalt ‘applications ‘On October 6, 2010, Avello Bioenegy (Ames, lowa) issued a press release that they had constructed a low load pavement using an asphalt binder extender developed at Iowa State University, The “Phase 2 Waveland Trail” bike tail was ‘constructed in the city of Des Moines usiag a binder formulsted with $ percent of a ‘material that is co-produced with pyrolysis oil (see penultimate column, Table 1). “The bike tail is 10 wide, 800 f long, and used a PG 58-28 binder KiOR Inc, (Pasadena, Texas) has developed a thermo-catalytic process for converting various sources of lignocellulose (eg wood chips, grasses) into renewable fuel blendstocks. They have been operating a 10 barrel per day (BPD) demonstration plant in Pasadena, Texas, for over 1S months This 4-story demonstration plant has been wsed to produce various matenals for the laboratory studies deseribed below. KiOR is currently constructing a 10-mmilion gal'year ‘commercial refwmery in Columbus, Mississipps, which iS on track to start up during the second half of 2012, Copyrighte ad mater Renewable Fuel Co-Products—Potential Uses in Asphalt 3, RENEWABLE FUEL CO-PRODUCT USE IN ASPHALT 3.1. troduction Considering the rmge in chemical composition available with the cellulosic pyrolysis processes and the volume of binder potentially available, an initial investigation of blending cellulosic pyrolysis bottoms with neat performance graded ‘binder was conducted. This evaluation included blending from 2 to 40 percent cellulosic pyrolysis bottoms oblained using different processing methods into a neat PG 64.22 The performance grading properties of the neat binder and the blends ‘were measured in accordance with AASHTO R 29, “Standard Practice for Grading ‘or Verifying the Performance Grade of an Asphalt Binder” (AASHTO, 2010), Laboratory mistures were made with the neat binder and each blend, and the ‘mixtures were subjected to moisture sensitivity testing in accordance with AASHTO. ‘T 283, “Standard Method of Test for Resistance of Compacted Asphalt Mixtures to ‘MoisturesInduced Damage” (AASHTO 2010). The sections that follow describe this evaluation, 3.2. Materials 5.21. Binders Table 4 summarizes the four different binders that were derived from lignoselluloses by either thermal or thermo-catalytic processing followed by some ‘ype of fractionation to isolate the high MW residue (binder) Examples | through 4 ‘were all proguced from Southem Yellow Pine chips. The chips were dried to 3 ‘nominal five weight pereen! moisture content and sized using a commercial hammer ‘mill to particle size less than $ mum. Example | is a bight esidoe from renewable emade For this example, the lignocefotose feedstock was converted thermo-ataytcally in a 10 BPD continuous Biomass Fluidized Catalytic Cracker (BECC™) using proprietary catalyst. The BFCC™ unit is described in the Appendix. Nest, the free water Dyproduct was separated from the ol by desanting. This material was then charged ‘to a wiped film evaporator (< 3 theoretical plates) and the high MW residue was ‘separated from the distilste at a presure of 10 torr” This rede (Example 1) hada ‘pomital initial boiling point (1BP) of 450°F by Simulated Distillation (SimDis) Example 2 isa heavy resktue from the same source. Example 2 was prepared in the same way as Example 1 except a bateh vacuum distillation unit was used (vs. 2 ‘wiped film evaporator) to isolate the high MW residue. This residve (Example 2) ‘had a nominal IBP of 650°F by distillation conditions (actual temperature and vacuum), Example 3 is a heavy residue from pyrolysis oil For Example 3, the lignocellulose feedstock was pyrolyzed using fluidized sand (no catalyst) asthe heat ‘wansfer media in a nit designed (o give equivalent yields tothe BECC™. As with a” Copyrighte ad mater TREWELLA, BONAQUIST, SANCHEZ Example 2, a batch vacuum distillation unit was used to isolate the high MW residue, Example 4 is a heavy reside from a hydrotreated renewable crude Like Examples | and 2, the lignocellulosic feedstock was converted thermo-catalytically in the BFCC™ using the same proprictary catalyst. After removing the free water ‘byproduct by decanting, the oil was fed to a fixed bed hydrotreater (HDT) where the ‘oxygen level was reduced (0 less than 0.5 percent. The HDT total Liquid product (TLD) was isolated from the gases by condensation. This TLP was then fractionated ‘ma batch vacuum distillation unit to produce a 630+ P residue The neat binder used in the evaluation was PG 64-22 obtained fam the Paulsboro, New Jersey, refinery of NuStar Asphalt, LLC, Table $ summarizes the performance grading properties of this binder. The neat binder has a continuous performance grade of PG 67.2 (20.8) 26.4, ‘Table 4, Summary of binders derived from renewable lignocellulosic feedstock, Example 1 | Example? [Example 3 [Example 4 ight Heavy Heavy KiOR Gas Description | Renewable | Renewable | Pyrolysis Oil | Out rude Crude Source Southern | Southem | Southem | Southern s Yellow Pine_| Yellow Pine_| Yellow Pine _ | Yellow Pine HeatSource | Reeenerted | Regenerated | Sand Regenerate wource | Catalyst | Catalyst Catabest Hydkoireater | None None None Yes Wipal Fim | Vacuum | Vaewom Vaewsn Fesseenties Distlation | Distiition | Distillation Nominal = 480 650 60 630 ‘Nominal Onuen we |S 1s » < 005 Water Se No No Yes No Furans, | Farans, | Anhydro | Aromatics Cuminant | phenols | Phenols | sugars ‘Cy-Pacattins si Levoglucosans 32 Copyrighted mater Renewable Fuel Co-Products—Potential Uses in Asphalt Table 5. Results of virgin PC 64-22 grading —— a SE a ate a Film Residue | \* Saas a Se can AASHTO T 315, 4300 ed ee es aise Asphalt Concrete Mixiure ‘A coarse, dense-graded 9.5 mm mixture composed of disbase coarse aggrezate, ‘and diabase and natural sand fine aggregate was used in the evaluation. This ‘misture Was selected because the dishase aggregate is moisture sensitive resulting 1n typical tensile strength ratios of approximately 70 percent when tested in accordance ‘wath AASHTO T 28% without antisiyp additives. ‘Table 6 summarizes pertinent volumetric properties ofthe mixture 3.3. Testing and Anatysis 3.3.) Initial Study In the initial stady, blends of 10, 20, and 40 percent of Example 1 cellulosic pyvolysis binder ina NuStar PG 64-22 were prepared and graded in secordance with ‘AASHTO R29. Example 1 fumed al temperatures higher than 120°C, therefor, the ‘blends were propared by heating both the cellulosic pyrolysts binder and the neat binder to 115°C and thea blending the materials for approximately 2 minutes using & ‘mechanical stiner. The performance grading properties of the blends are summarized in Table 7 Figures 1, 2, and 3 show the effect of increasing concentration of Example | cellulosic pyrolysis binder on the high, intermediate, nl low temperature propeties. Copyrighte ad mater TREWELLA, BONAQUIST, SANCHEZ Table 6 Mixture volumetric properties. Property Value Sieve Sue. mm 123 100 38 oR 475 33 ello 236) 40 Lia 3 0.600 22, 0.300 2 0.150 7 0.075 ae ‘Asphalt Content, 6 37 Nicos 100 ‘Design VIM. %, 37 ‘Design VMA.% 151 ‘Design VFA, % 755 ‘Dust fective Binder Ratio 10. Fine Ageregate Angularty, a83 ‘Coarse Aggregate Angularity, % 100/100 Fiat and Elongated Particles, % 16 ‘Sand Equivalent 767 Increasing the concentration of Example 1 cellulosic pyrolysis binder decreased ‘the high temperature grade based on tank dynamic shear rheometer (DSR) ‘measurements, increased the high temperature grade based on rolling thn film oven. fest (RIFOT) residue DSR measurements, increased the termediate grade temperature, and increased the low temperature grade. From Figures 1, 2, and 311 ‘was estimated that $ percent is the maximum amount of Example 1 cetlulesic pyrolysis binder that can be added without making a change st the performance grade of the blended binder Fer this concentration, the continuous performance ‘grade was estimated to be PG 66 (25) 24 Moisture sensitivity testing was then performed in accordance with AASHTO. ‘T 283 on the Virginia diabase misture using the neat NuStar PG 64.22 binder and 8 5 percent blend of Example 1 cellulosic pyrolysis binder in NuStar PG 64-22. The ‘results are summarized in Table ®. Adding S percent Example | cellulosic pyrolysis binder improved the tensile strength ratio from 70 to 83 percent. ‘These results were ‘encouraging and indicated that cellulosic pyrolysis binder could be used to improve the resistance of mixtures to moisture damage Copyright $ material Renewable Fuel Co-Products—Potential Uses in Asphalt am of ay omens as 399 Tea xe Toe says imon ASE O/ S08 Ban ce ray amssany OLS so sea Sore Sento a it om 35 Taney shoved ween Sues spweyy | alors] of saysadoud Supous smmanied fo Cowan 4 90, 6 material Copyrighte TREWELLA, BONAQUIST, SANCHEZ omens amorand ‘not 3c Pras ne Cnet Figure 1. Effect of Example I cellulosic pyrolysis binder on high temperature grade. i ert Conan Side ptt * aml a Py da Cone Figure 2 Effect of Example 1 cellulosic. pyrolysis binder on mtcrmediate temperature grade Copyrighted material Renewable Fuel Co-Products—Potential Uses in Asphalt ‘anole Candee Preys er Cate, Figure 3. Effect of Example 1 cetivlosic pyrolyse binder om low temperature spre: 37 TREWELLA, BONAQUIST, SANCHEZ ‘Table &, Summary of AASHTO T 283 testing for Example 1 Ci pra bade, Gesor, | pecines sirvoids, | Saaraon, | Tem sn PE | seen Teas Spy sa 6a Naw Brersge—] 7 io Niser [1 —[Conitiveed | 7420 poeta [2 | conitonss | 74 Tas 4 [een] 73 [63 average | 74 TSR | oar Teas [py [97s 5 7 oe ES Nese mrenge—| 78 Ws Ro 64az [7 [conned | 74] 51 [9883 eres [| Combos [74] 725 : 6 [eontsieea| 75 | 717 average 74 TSR Ratio | W.3% NA= not applicable 5.5.2 Process Changes ‘The inital study was encouraging It showed that cellulosic pyrolysis hinder has ‘the potential 19 be used as a paving binder extender and to impart improved resistance 10 moisture damage. The initial study also identified wo areas of improvement for use as an asphalt extender with antistripping properties. First, Example 1 fumed at temperatures well below normal asphalt mixing temperatures, releasing an odor that was serid in mature unlike the smell of asphalt binder ‘Second, there was significant stiffening of the blended binder upon conditioning in the RTFOT, indicating that there may be rapid aging of the blended binder during ising ‘To adéress these issues, additional examples of cellulosic pyrolysis binder were ‘prepared by modifying the fractionation of the binder. Example 2 isthe same as Example 1 except the initial boiling point was increased from 4S0°F to 6S0°F (see Copyright $ material Renewable Fuel Co-Products—Potential Uses in Asphalt Table 4) This resulted im a binder having no odor and less potential for volatilization at typical HMA temperatures New, in order to alter the chemical composition in EXample 3, the catalyst was replaced with sand, This shifts the process chemistry from thermo catalytic to ‘essentially 100 percent thermal pyrolysis) and leads to a material having 3 ‘sgnificantly higher concentration of oxygen, typically between 44 and 60 percent (Charon, 2009). In addition, the majority of this osygen is present as ankydro ‘sugars. Patwanuhan et. Al, have reported that the fast pyrolysis (sand) of cellulose produces a product in which 67.2 percent of the identified compounds are anhyilro ‘sugars (Patwardhan etal .2009), In Example 4, the composition was modified by hydrotreating using a commercial hyrotreating catalyst Hydrotreating removes essentially all the Iheteroatoms, producing a very clean heavy hydrocarbon gas oil product, Example 2, Example 3, and Example 4 cellulosic pyrolysis binders were blended fat 5 percent concentration with neat NuStar PG 64-22 binder and graded in ‘accordance with AASHTO R 29. For each of these a 20 percent concentrate was prepared by heating both the cellulosic pyrolysis binder and the neat binder to 175°C ‘an mixing for 30 minutes wath a mechanical stirrer. Afr the concentrate cooled, it ‘was reheated to 160°C and additonal neat binder also beated to 160°C was added to wach the target concentration of S percent. Table 9 summarizes the results of the Performance grading for these examples. Figures 4, 5, and 6 compare the performance grading These figures include the data forthe neat PG 64-22 and each ‘Of the four § percent cellulosic pyrolysis biader blends. Figure 4 shows that Example I and Example 4 decrease the high temperature grade of the blended binder, while Example 2 and Example 3 increase the high temperature grade, The ‘aging effect described cantcr in the initial study is clearly evident in Figure 4. The high temperature grade based on RTFOT aging is much higher for Example 1 compared to the neat PG 64-22. This effect was improved in Example 2 and Example 3 and is not evident im Example 4. Figure 5 shows the effect of the various cellulosic pyrolysis binders on the intermediate grade Example 1, Example 2. and ‘Example 3 increase the intermediate grade temperature, while Example 4 decreases ‘I fact, for Example 2, the intermediate grade temperature controls the tow temperature grading of the blended binder. The effect of cellulosic pyrolysis binder ‘on the low temperature grade i illustrated in Figure 6, This eect is similar to the effect on the intermediate grade Example 2 and Example 3 inerease the low temperature erade while Example 4 decreases it, All cellulosic pyrolysis binders ‘make the low temperature properties of the binder somewhat mone m-value ‘controlled, Copyrighte ad mater ‘TREWELLA, BONAQUIST, SANCHEZ eet a a ‘OSV wena — | — smeend Re LOSE 0 ERO MS ARIA) SEIKI J99%) apera pee nae ae ste roussey | EVM = ee Pay wr ste Lous | sapany a aE OF conan | mane e oo ae ae a wt " FL = te a ae Fa ywe— pms yeme | ease wn, — IE+9Dd ASO EID" AMISH wir99d isan | wk - ropduaonsy pun gayduussy coydwunns fo spuryg mosied ¢ sof sonsadoud Suapest sounnuofied fo Canuuns.'6 148, $ material Copyrighted Renewable Fuel Co-Products—Potential Uses in Asphalt je { i ih. , Figure 4, Effect of cellulosic pyrolysis ber om high temperature grade, ntrmeite Ymprtre rae, i der tote Figure 5. Effect of cellulosic pyrolysis binder om intermediate lemperature grade. material TREWELLA, BONAQUIST, SANCHEZ Figure 6. Eifect of cellulosic pyrolysis binder on low temperature grade ‘Compared to typical petroleum binders that have Jess than 3 percent oxygen, ‘Examples 1 through 3 each have a very high coneentration of elemental oxygen (15+ 3ano) Ths osyen i presen ax organi oxygen compounds ofthe yes inten For the renewable crude residues (Examples 1 and 2) we observe both phenols, and furans by miclear magnetic resonance (NMR), Both of these species ate good H-bond acceptors and cam fonm higher MW aggregates with H-bond donors Phenols are H-bond donors and are therefore able to associate with the H-bond accepior moiety of furans and other phenols. The dynamic association and disassociation of these H-bonding aggregates is exothermic and endothermic, respectively. Iti therefote likely that these processes ate affecting the theological behavior of the binders Non-calalytic pyrolysis residues (Example 3) have a high concentration of ‘anhydro sugars such as levoglucosan as shown in Figure 7. Like phenols, these species are both H-bond acceptors and H-bond donors and are therefore also able 10 selb-assoviate. Here again, the dynamic association of these H-bonding aggregates, is exothermic and the disassociation is endothermic, affecting the rheological ‘bchavior of the binders an Copyrighted mater Renewable Fuel Co-Products Potential Uses in Asphalt OH 0. P )»o4 OH Figure 7. Structure oflevogluscosn Unlike Examples 1-3, Example 4 is essentially free of oxygen-containing compounds also has only parts per mullion levels of nitrogen, sulfur, and metals Its therelore more akin to a petrolewn maltene fraction than the other examples We believe that these differences account for the differeat behavior of this example ‘compared to the other examples with regard to intermediate and low temperature theology. AASHTO 283 moisture sensitivity testing was also conducted on the $ percent ‘blends of the various cellulosic pyrolysis binders. The results are summarized 1m ‘Table 10. Figure 8 compares the tenale siength ratio of the neat PG 64-22 and all ‘of the cellulosic pyrolysis binders. All the cellulosic pyrolysis binders improved the ‘resistance of the mixture to moisture damage For Examples 1 through 3, we attribute this benefit to the H-bonding ability of the orgame oxyzenates. As with conventional amine-based anitstrippmg additives, polar compounds like these can compete effectively with water to H-bond to polar sues on the surface of the aggregate. In addition when a segment of the organic ‘oxygenate molecule is hydrophobic, the compound can be ambiphiic and act as a ‘compatabilizer. In this way it bridges between the polar aggregate surface and the ‘much less polar hydrocachon binder In the eave of Example 4, beeanse of the low heteroatom content, the enbanced ‘water resistance performance must stem ftom a diferent mechanisen. ‘This may be dae to aromatic ring charge transfer complexes with the surface ofthe aggregate ‘Additional studies are needed. Copyright $ material TREWELLA, BONAQUIST, SANCHEZ Table 18. Summary of AASHTO T283 testing Binder Specimens | Condition: Voids, satiate in |e 2 Dry 42 NA eee ee PS Ns AN 42 eee Example s Conditioned UW 734 cat == —t ee ete : AY 68 rosie: |-—5—Taanineer es [a : Ps Bomb’ 3 Conditioned 69 TIS. ete a ee ets = Average 65. Wooten [7 —T eonttins | 66 |S i Sees ee eee ee meee a ‘NA® not applicable. Copyrighted material Renewable Fuel Co-Products—Potential Uses in Asphalt Tene Siren ai, eezxsaaez & 8 Cours! SMtuanpleL SKfuample? Sk Eales Figure 8. Fer of cellulosic pyrolysis binders on moisture sensitivity. Figure 9 compares the tensile strengths forthe cellulosic pyrolysis binders with that forthe neat PG 64-22 binder. The tensile strengths zenerally follow the high ‘temperature stilfiness ofthe binder. Example 2 and Example 3. which inerease the hhigh temperature grade of the blended binder, produced mixtures with higher tensile strength than the control. Example 1 and Example 4, which decrease the high ‘temperature grade of the blended binder, produced mixtures with lower tensile strengths 4. FUTURE WORK, As shown above, we have demonstrated that it i possible w produce an ‘enhanced asphalt binder material having added benefits during the thermo-cataytie conversion of lignocellulose to renewable liquid transportation fuels, Copyrighted material a 8 Tone Sent 8 & TREWELLA, BONAQUIST, SANCHEZ Sangh endmanet tenth Gavel Stumps SSitampe 2 SMe SK amples wieure Figure 9. Lifect of celluioste pyrolysis bunders on tensile strength. ‘There are many process variables that can be altered to change the properties of the high MW binder that is co-produced during the manufacture of liquid transportation fuels In this study we only explored the impact of three variables, residue initial boiling point, presence or absence of catalyst, and hydoweatine ‘Many additional process variables cau be explored. These inchude Feedstock type Feedstock pretreatment (e g. pereent waler) BFCC™ catalyst formulation Catalyst : feedstock ratio BFCC™ riser top temperature BFCC™ catalyst make-up rate BFOC™ renewable crude fractionation BRCC™ renewable crude fractionation priot to hydrotreating an HDT catalyst formulation 10, HDT seventy I one were 10 explore all combinations of each of these ten variables a just wo “levels” st would correspond to 1024 experiments (2"°). With this many: process qt high, bles to capitalize on, the prospects for producing valuable binder materials are Copyright smal al Renewable Fuel Co-Products—Potential Uses in Asphalt 5, REFERENCES, Anex RP. Aden A. Kari EK, Fortman J. Swanson RM, Wright MM. Sato JA, Brown RC. Daugased DE, Plaon A, Kothandaramay G, Hse DD, Duwa A. “Techao-ecovomic Comparison of Biomass-o-Teansportaton Foels via Pyrolysis Gasification and Biochemical Pathways.” Fuel (2010), dot 10.1016 fel 2010.07 015 Charon N_ Omas B. Pinheiwo A. Courtinde M. Ponthus J. Espinat D. Quignand A. “investigation of Fast Pyolyas Oils Composiion by Fractionation, GE

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