Sterol blends as additives in asphalt binders.

Abstract

To provide compositions and methods for retarding, reducing or enhancing the effects of aging in recycled or reclaimed asphalt to retain or restore some or all of the original properties of virgin asphalt binder. [Solution] Provided is an asphalt binder composition comprising a virgin asphalt binder, an aged asphalt binder, or both, and a pure sterol:crude sterol blend, the sterol blend comprising a weight ratio of pure sterol to crude sterol of 10:90 to 90:10, the sterol blend being present in an amount effective to impart a less negative ΔTc value and a reduced R value to the aged asphalt binder composition compared to a similarly aged asphalt binder without the sterol blend.

Description

[Technical field]

[0001] CROSS REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Application No. 62 / 372,504, filed Aug. 9, 2016, the disclosure of which is incorporated herein by reference. [Background technology]

[0002] Asphalt pavement material is one of the most recycled materials worldwide, finding applications when reused in pavement surfaces and bridge abutment shoulders, as a gravel substitute in unpaved roads, and as a replacement for unused aggregates and binders in virgin asphalt pavements. Generally, the applications of recycled asphalt pavement material are limited to pavement layers below the surface, or to limited amounts of asphalt base and surface layers. Such applications are limited because asphalt deteriorates over time, losing its stress relaxation, oxidizing and embrittling, and may become prone to cracking. These results are primarily due to the aging of organic components in asphalt (e.g., bitumen-containing binders), especially due to exposure to environmental factors. Aged binders are also very viscous. As a result, reclaimed asphalt pavement material has different properties than virgin asphalt and must be processed to prevent the properties of the aged binder from affecting long-term performance.

[0003] A number of materials have been investigated to reduce or delay the effects of asphalt aging on the long-term performance of the mix. For example, rejuvenation additives are marketed with the express purpose of reversing the aging that occurs in recycled raw materials (e.g., recycled asphalt pavement (RAP) and / or recycled asphalt shingles (RAS)). It is plausible that no asphalt restoration may actually occur, and that these additives act as softeners for the virgin binders used in mixes containing RAP and / or RAS. In some cases, 10% by weight or more of these softeners are added to the virgin binders when such mixes are manufactured. Aging can be evaluated by measuring ΔTc (the difference between the stiffness critical temperature and the creep critical temperature after aging). The use of softeners can produce mixes with regenerated binder properties that exhibit acceptable ΔTc even after extended periods of aging the mix. However, these acceptable binder properties after aging are obtained at the cost of producing mixes whose stiffness may decrease significantly during the early years of paving. Summary of the Invention

[0004] Disclosed are compositions and methods for retarding, reducing or enhancing the effects of aging in recycled or reclaimed asphalt to retain or restore some or all of the original properties of the virgin asphalt binder.

[0005] In one embodiment, the present disclosure provides a method of retarding or repairing the aging of an aged asphalt binder comprising adding a pure sterol:crude sterol blend to an asphalt binder composition comprising virgin asphalt binder, aged asphalt binder, or both, the sterol blend comprising a weight ratio of pure sterol to crude sterol of 10:90 to 90:10.

[0006] In one embodiment, the present disclosure provides a method of recycling aged asphalt binder for asphalt binder pavement production comprising adding a pure sterol:crude sterol blend to an asphalt binder composition comprising virgin asphalt binder, aged asphalt binder, or both, the sterol blend comprising a 10:90 to 90:10 weight ratio of pure sterol to crude sterol.

[0007] In another embodiment, the present disclosure provides an asphalt binder paving composition comprising a virgin asphalt binder, an aged asphalt binder, or both, and a pure sterol and crude sterol blend, the sterol blend comprising a pure sterol to crude sterol weight ratio of 10:90 to 90:10.

[0008] In yet another embodiment, the present disclosure provides a method of rehabilitating aged asphalt binder comprising adding a pure sterol:crude sterol blend to the reclaimed asphalt binder, the sterol blend comprising a weight ratio of pure sterol to crude sterol of 10:90 to 90:10. [Brief description of the drawings]

[0009] [Figure 1] FIG. 1 shows a representative plant sterol structure (eg, beta-sitosterol). [Diagram 2] FIG. 2 is a graph showing stiffness and creep temperature results for re-refined engine oil bottoms (REOB) blends having sterols. [Diagram 3] FIG. 3 shows typical plant sterols. [Figure 4] FIG. 4 is a graph showing stiffness, m-value critical temperature and ΔTc for PG64-22+8% REOB and 10% of blends of various concentrations of tall oil pitch and sterols. [Diagram 5] FIG. 5 is a graph showing a comparison of ΔTc for PG64-22 + 8% REOB + three levels of pure sterols and PG64-22 + 8% REOB. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The disclosed asphalt compositions contain anti-aging (i.e., reduce or delay aging) sterol blends that aid in the preservation, recycling, and reuse of the asphalt compositions. The asphalt compositions are preferably free of cyclic organic compositions, including esters or ester blends. The disclosed compositions have particular value in the reclaiming of asphalt, particularly asphalt that contains softeners such as waste engine oil.

[0011] The disclosed asphalt compositions provide recycled asphalt binders that may have improved physical and rheological properties, such as stiffness, effective temperature range, and low temperature properties. Some embodiments provide for the use of binders extracted from recycled asphalt pavement, recycled asphalt shingles, or both in asphalt blends. Some embodiments provide for the addition of sterol blends that allow for high stiffness at high temperatures while minimizing potentially detrimental low temperature effects of recycled asphalt.

[0012] The headings provided herein are for ease of reading only and are not to be construed as limiting.

[0013] (Abbreviations, Acronyms and Definitions) "Aged asphalt binder" refers to asphalt or binder present in or reclaimed from recycled asphalt. Aged binders have a higher viscosity compared to that of virgin asphalt or virgin bitumen as a result of aging and exposure to ambient temperatures. "Aged binder" refers to virgin asphalt or virgin binder that has been aged using the laboratory aging test methods described herein (e.g., RTFO and PAV). "Aged binder" can also refer to virgin binders that are hard, poor quality, or out of specification and can be improved by adding the blends disclosed herein, particularly virgin binders that have a ring and ball softening point of 65°C or greater according to EN1427 and a permeability value at 25°C according to EN1426 of 12 dmm or less.

[0014] "Aggregate" and "construction aggregate" refer to particulate mineral materials, such as limestone, granite, trap, gravel, crushed gravel, sand, crushed stone, crushed rock and tailings, that are useful in paving and paving applications.

[0015] "Asphalt binder" refers to a binder material containing bitumen and optionally other ingredients suitable for mixing with aggregates to produce a paving mixture. Depending on local usage, "bitumen" may be used interchangeably or as a substitute for "asphalt" or "binder."

[0016] "Asphalt pavement" refers to a compacted blend of asphalt and aggregate.

[0017] "Asphalt paving mix", "asphalt mix" and "mixture" refer to a mixture of uncompacted asphalt and aggregate. Depending on local usage, "bitumen mix" or "bituminous mixture" may be used interchangeably or as a substitute for "asphalt paving mix", "asphalt mix" or "mixture".

[0018] "Bitumen" refers to a naturally occurring or manufactured, primarily high molecular weight hydrocarbon, black or dark-colored (solid, semi-solid or viscous), cementitious material, typical of which are asphalt, tar, pitch and asphaltenes.

[0019] "Crude" when used in reference to a material containing a sterol means a sterol that has not been fully purified and may contain additional components in addition to the sterol. "Neat" or "Virgin" means that the material has not yet been used in asphalt pavement or asphalt shingles or has been recycled from asphalt pavement or asphalt shingles and may include performance grade binders.

[0020] "PAV" refers to the Pressurized Aging Vessel test. The PAV test promotes the accelerated aging of asphalt as described in ASTM D6521-13, Standard Practice for Accelerated Aging of Asphalt Binder Using a Pressurized Aging Vessel (PAV).

[0021] When applied to a sterol or mixture of sterols, "pure" means having at least technical grade purity or at least reagent grade purity.

[0022] "Reclaimed asphalt" and "recycled asphalt" refer to RAP, RAS and old pavement, shingle manufacturing waste, roofing felt and other products or applications.

[0023] "Reclaimed asphalt pavement" and "RAP" refer to asphalt that has been removed or excavated from a previously used road or pavement or other similar structure and processed for reuse by any type of known method, including grinding, splitting, breaking, crushing or pulverizing.

[0024] "Reclaimed asphalt shingles" and "RAS" refer to shingles that are derived from sources including roof tear-off, manufacturer's waste asphalt shingles and post-consumer waste.

[0025] "RTFO" refers to the Rolling Thin Film Oven Test. RTFO is a test to simulate short-term aging of asphalt binders as described in ASTM D2872-12e1, Standard Test Method for Effect of Heat and Air on a Moving Film of Asphalt (Rolling Thin-Film Oven Test).

[0026] "Softener" refers to an additive that facilitates (or promotes) the mixing and incorporation of recycled asphalt into new bitumen or asphalt mixes during the asphalt mix manufacturing process.

[0027] "Sterol blend" refers to compositions, mixtures, and blends of pure and crude sterols that can be combined with aged binders (e.g., recycled or reclaimed asphalt) to slow the aging of the asphalt binder or to retain or restore some or all of the original properties of the virgin asphalt or virgin binder.

[0028] "ΔTc" refers to the difference between the stiffness critical temperature and the creep critical temperature. The stiffness critical temperature is the temperature at which the binder has a flexural creep stiffness of 300Mpa when tested according to ASTM D6648, and the creep critical temperature is the temperature at which the slope of the flexural creep stiffness versus creep time when tested according to ASTM D6648 has an absolute value of 0.300. Alternatively, the stiffness critical temperature and the creep critical temperature can be determined by the 4mm Dynamic Shear Rheometer (DSR) testing and analysis method described in Sui, C., Farrar, M., Tuminello, W., Turner, T., A et al., "New Technique for Measuring low-temperature Properties of Asphalt Binders with Small Amounts of Material, Transportation Research Record: No1681, TRB 2010." See also Sui, C., Farrar, MJ, Harnsberger, PM, Tuminello, WH, Turner, TF, et al., "New Low Temperature Performance Grading Method Using 4 mm Parallel Plates on a Dynamic Shear Rheometer." In "TRB Preprint CD, 2011," the stiffness critical temperature is the temperature at which the relaxation modulus equals 143 MPa, and the creep critical temperature is the temperature at which the absolute value of the slope of the master curve of relaxation modulus versus relaxation time equals 0.275.

[0029] All weights, parts and percentages are by weight unless otherwise stated.

[0030] (Binder) Current bitumen paving techniques include the use of high percentages of RAP and / or RAS as ingredients in the bitumen being paved. Typically, RAP concentrations can reach 50% and RAS concentrations can reach 6% by weight of the paving mix. A typical RAP has a bitumen content of 5-6% by weight and a typical RAS has a bitumen content of 20-25% by weight. As a result, a bitumen mix containing 50% RAP by weight will have 2.5%-3% RAP bitumen contributed to the final bitumen mix, and a bitumen mix containing 6% RAS by weight will have 1.2%-1.5% RAS bitumen contributed to the final bitumen mix. In many instances of both RAP and RAS, recycled additives are combined into the binder mix; for example, 20%-30% RAP and 5%-6% RAS are incorporated into the binder mix. Based on typical binder contents of RAP and RAS, a binder mix containing 20%-30% RAP and 5%-6% RAS can result in as much as 2%-3.3% binder (by total mix weight) coming from the combination of RAP and RAS. A typical bituminous paving mix contains about 5.5% total bitumen, so there can be as much as about 36%-60% total bitumen in these bitumen mixes from recycled sources.

[0031] The properties of bitumen in these reclaimed resources relative to the virgin binders used in the bituminous mixtures are shown in Table 1. To determine the ΔTc parameters, the Western Research Institute 4 mm Dynamic Shear Rheometer (DSR) testing method and data analysis method were employed (see Sui, C., Farrar, M., Tuminello, W., Turner, T., A New Technique for Measuring low-temperature Properties of Asphalt Binders with Small Amounts of Material, Transportation Research Record: No 1681, TRB 2010; see also Sui, C., Farrar, MJ, Harnsberger, PM, Tuminello, WH, Turner,TF, New Low Temperature Performance Grading Method Using 4 mm Parallel Plates on a Dynamic Shear Rheometer. TRB Preprint CD, 2011).

[0032] [Table 1] Table 2 shows the high and low temperature properties of blends made with virgin binder and bitumen reclaimed from post-consumer waste shingles after different periods of aging. Also shown in Table 2 are the high and low temperature properties of mixtures containing RAP and / or RAS. Some of these mixtures underwent extended laboratory aging and some were obtained from field cores.

[0033] [Table 2] Tables 1 and 2 show the impact of incorporating recycled materials, particularly post-consumer waste shingles, at high binder substitution levels. The data indicate the desirability of incorporating additives into the bitumen and bitumen blends to mitigate the effects of bitumen from these recycled components and retard further oxidative aging of the total bitumen in the final blend. The last three columns of Table 2 show that the further away from the air-mixture interface, the smaller the impact on the ΔTc parameter. This parameter can be used to assess the effect of aging on binder properties, and more specifically, on the flexural properties of the binder; the flexural properties are characterized by a property referred to as the "low temperature creep grade."

[0034] A study published in 2011, based on data from reclaimed binders from field cores, showed that ΔTc is used to identify when a pavement has reached a point where it is at risk of cracking for non-load related mixes and when it has reached a potential failure limit. In that study, the authors subtracted the stiffness critical temperature from the creep temperature and m-critical temperature, resulting in a ΔTc value that is positive for binders with poor performance characteristics. A 2011 industry survey agreed to reverse the order of subtraction, thus producing a negative ΔTc value, indicating poor performance characteristics, when the m-critical temperature is subtracted from the stiffness critical temperature binder. The industry generally agreed that poor performing binders would be more negative as the degraded performance seemed more intuitive. Thus, in the industry today, and as used in this application, the warning limit for ΔTc is -3°C and the potential failure value is -5°C. In other words, -5°C is more negative than -3°C, and therefore, the ΔTc value for -5°C is worse than the ΔTc value for -3°C.

[0035] Reports at two Federal Highway Administration Expert Task Force meetings demonstrated a correlation between ΔTc values ​​of binders reclaimed from field test projects and the severity of pavement damage associated with fatigue cracking. Furthermore, when the binders used to construct these field test projects were subjected to 40 hours of PAV aging, ΔTc values ​​correlated to pavement damage associated with fatigue cracking, particularly downward fatigue cracking, which is generally believed to be a result of loss of binder relaxation at the bituminous mix surface.

[0036] It would therefore be desirable to have bituminous mixtures containing bituminous materials that have reduced sensitivity to the development of excessively negative ΔTc values.

[0037] The data in Table 1 show that typical virgin binders produced in refineries can maintain a ΔTc above -3°C after 40 hours of PAV aging. The data in Table 1 further show that binders regenerated from RAP have a ΔTc below -4°C, indicating that the impact of high RAP levels in fresh bitumen mixtures should be evaluated. Furthermore, the extremely negative ΔTc values ​​for the RAS regenerated binders require further scrutiny of the overall impact of RAS incorporation in bitumen mixtures.

[0038] Table 2 shows that it is possible to perform reclamation of binder from the mixture after aging of bituminous mixtures in laboratory aging and to measure the ΔTc of the reclaimed binder. The procedure for long-term aging of bituminous mixtures in AASHTO R30 details aging of compacted mixtures for 5 days at 85°C. Some research studies have extended the aging time to investigate the effects of more severe aging. Recently, aging of vanished bituminous mixtures at 135°C for 12 and 24 hours has been shown as an option for aging compacted mixtures for longer periods in some instances. The goal of these aging protocols is to produce rapid binder aging similar to that typical of field aging for 5 years or more of service, and more preferably 8 to 10 years of service. For example, the ΔTc of reclaimed or recycled asphalt extracted from the top 1 / 2 inch of pavement was more severe than aging for 12 hours at 135°C, but less severe than aging for 24 hours at 135°C.

[0039] The data in the first two columns of Table 2 show why extended aging of the mixtures containing recycled products is important: the binder regenerated from the unaged mixture (column 1) exhibited a ΔTc of -1.7°C, while the binder regenerated from the 5 day aged mixture exhibited a ΔTc of -4.6°C.

[0040] (Pure Sterols: Crude Sterol Blend) The disclosed sterol blends (pure sterols: crude sterols) can alter (e.g., reduce or slow) the aging rate of asphalt binders, or repair or regenerate aged or recycled binders to exhibit some or all of the properties of virgin asphalt binders. For example, the sterol blends can modify or improve the physical or rheological properties, such as the stiffness, useful temperature range, and low temperature properties of the asphalt binder.

[0041] In some embodiments, the sterol blend belongs to the class of triterpenoids (especially sterols or stanols). The disclosed blends (e.g., triterpenoids) can function effectively with asphaltenes. Asphaltenes encompass a broad range of fused ring systems with some level of unsaturation. The asphaltene content of a typical binder can range from less than 10% to more than 20%. Asphaltenes are generally described as materials that are insoluble in n-heptane. The exact structure is unknown and based on the performance behavior of different binders, it is unlikely that the structure of asphaltenes in any two binders, especially those derived from different crude sources, will be identical. Asphaltenes result in binders whose color and stiffness and their amount in the binder increases as the binder ages. In conclusion, the addition of RAP and / or RAS or a combination of both causes an increase in asphaltene content. The increase in asphaltene content along with other oxidation products such as carbonyls and sulfoxides is responsible for the stiffness of the bitumen mixture and its eventual failure. By their very chemical nature, asphaltenes are not readily soluble in aliphatic compounds. Aromatic carbohydrates readily dissolve asphaltenes, and aromatic process oils have been used in recycled blends. However, these oils contain polynuclear aromatic compounds, including the potential carcinogens listed, and therefore are not preferred additives. Most vegetable-based oils are straight or branched chain hydrocarbons with some level of unsaturation, and therefore are not effective in slowing aging in the overall softening of the binder in the blend.

[0042] Triterpenoids are a major group of natural plant products, including sterols, triterpene saponins, and related structures.Triterpenoids can be of natural or synthetic origin.Typically, they are obtained by extraction from plant material.Extraction processes for isolating triterpenoids are described, for example, in International Application WO2001 / 72315A1 and WO2004 / 016336A1, each of which is incorporated herein by reference in its entirety.

[0043] Triterpenoids encompass plant sterols and plant stanols. The disclosed triterpenoids refer to the unesterified form of any plant sterol or stanol described herein.

[0044] Exemplary plant sterols include campesterol, stigasterol, stigmasterol, β-sitosterol, Δ5-avenosterol, Δ7-stigasterol, Δ7-avenosterol, brassicasterol, or mixtures thereof. In some embodiments, the sterol blend includes β-sitosterol as the deuterium sterol. Commercially available pure sterols and blends of pure sterols include those available from MP Biomedicals (catalog number 02102886), referred to as β-sitosterol (β-sitosterol ~40-60%; campesterol ~20-40%; campesterol ~5%). In some embodiments, the pure sterol has at least 70% sterol by weight, and in some embodiments at least 80%, at least 85% or at least 95% by weight.

[0045] Exemplary crude plant sterols include modified or unmodified natural products that contain significant amounts of sterols, and include such diverse plant sources as corn oil, wheat germ oil, sarsaparilla root, soybean pitch, and corn oil pitch. For example, tall oil pitch is obtained during the processing of wood, particularly pine wood, to prepare paper. Tall oil pitch contains rosin, fatty acids, oxides, esterified materials, and to a significant extent, sterol esters. Plant sources of crude sterols are not expensive in that they are the foots or tailings left over from various manufacturing processes. In some embodiments, the crude sterol source includes stigmasterol, β-sitosterol, campesterol, ergosterol, brassicasterol, cholesterol and lanosterol or mixtures thereof. In some embodiments, the crude sterol source includes soybean oil, corn oil, rice bran oil, peanut oil, sunflower seed oil, safflower oil, cottonseed oil, rapeseed oil, coffee seed oil, wheat germ oil, tall oil and wool fat. In some embodiments, the crude sterol includes a biosource or a partial distillation residue of a biosource. In some embodiments, the crude sterol includes tall oil pitch, soybean oil or corn oil.

[0046] Oil tailings or pitch from the disclosed plant sources are a suitable source of crude sterols. U.S. Patent No. 2,715,638 (August 16, 1955, Albrecht) discloses a process for recovering sterols from tall oil pitch whereby fatty acid impurities are removed by a neutralization process. According to this, the sterol esters are saponified and the free sterols are subsequently recovered, washed with isopropanol, and dried. If sufficiently purified, the recovered free sterols may be used as pure sterols rather than as crude sterols in the disclosed pure sterol:crude sterol blends. The crude sterol is preferably obtained from a plant source. The crude sterol may contain components in addition to the desired sterol or sterols. Exemplary plant sources for crude sterol include tall oil pitch, crude tall oil, sugar cane oil, hot well skimmings, cottonseed pitch, soybean pitch, corn oil pitch, wheat germ oil, or rye germ oil. In some embodiments, tall oil pitch is the source of crude sterol. Tall oil pitch may contain about 30-40% unsaponifiable molecules. Unsaponifiables are molecules that do not react with alkali hydroxides. The retained fatty acids and rosin acids in tall oil pitch react easily with potassium hydroxide or sodium hydroxide, so that the unsaponifiables can be easily separated. It has been shown that 45% of the unsaponifiable fraction may contain sitosterol. Thus, tall oil pitch samples may contain approximately 13.5%-18% sterol molecules by weight. In some embodiments, the crude sterol may have a purity less than food grade (e.g., 85% sterol by weight) or may contain more than 85% sterol by weight and may also contain impurities or contaminants that render the material unsuitable for food use.

[0047] In some embodiments, the crude sterol may be derived from an animal, such as cholesterol.

[0048] The pure sterol:crude sterol blend added to the asphalt composition may range, for example, from about 0.5 to about 15%, from about 1 to about 10%, or from about 1 to about 3% by weight of the virgin binder in the asphalt composition. In some embodiments, the sterol blend may include a ratio of pure sterol to crude sterol of 10:90 to 90:10. In some embodiments, the sterol blend may include a ratio of pure sterol to crude sterol of at least 20:80, 30:70, or 40:60. Additionally, in some embodiments, the sterol blend may include a ratio of pure sterol to crude sterol of less than 80:20, 70:30, or 60:40.

[0049] In some embodiments, the pure sterol:crude sterol blend may modify, reduce, or delay degradation of rheological properties in binders containing recycled bitumen materials, including softeners (e.g., RAS, RAP, REOB, virgin paraffinic or naphthalene base oils, untreated or unrefined waste drain or waste engine oil materials, vacuum tower asphalt extenders, paraffinic or naphthalene process oils, or lubricant base oils). In some embodiments, the sterol blend when used in asphalt or asphalt pavement maintains a ΔTc of -5°C or greater as the asphalt or asphalt pavement is aged.

[0050] In some embodiments, the pure sterol:crude sterol blends can result in asphalt binder compositions having a ΔTc of -5.0° C. or greater. In some embodiments, the sterol blends can result in asphalt binders having a ΔTc of -5.0° C. or greater after 40 hours PAV aging. In yet other embodiments, the disclosed sterol blends can result in binders having a less negative ΔTc and reduced R-values ​​after aging when compared to binders aged in the same manner without the sterol blend.

[0051] (Softeners and other additives) Softeners that can be used in the binder include waste engine oil and waste engine oil that can be further processed to obtain REOB. REOB is an inexpensive softening additive and asphalt extender obtained from the residues kept after distillation of waste engine oil either under vacuum or atmospheric conditions. The distillate fractions from the re-refining process are reprocessed into new vehicle lubricants, but the bottoms have no available market due to the presence of metals and other particles from the internal combustion engines. These bottoms also contain paraffinic hydrocarbons and additives that were incorporated into the original lubricants. For many years, REOB has been used by some companies as an asphalt extender, but the use has been localized.

[0052] Large amounts of waste engine oil are being manufactured and sold in the asphalt binder market as REOB. The use of REOB results in mixes that, when aged, have ΔTc values ​​below -4°C, resulting in inferior performance in paving. When REOB is added to some asphalts at levels as low as 5% by weight, it results in a ΔTc after 40 hours. PAV aging can be below -5°C (i.e., more negative). Binders reclaimed from field mixes shown to contain REOB by means of metallurgical testing showed greater damage than field mixes of the same age and paved with the same aggregate and time but without REOB.

[0053] The disclosed pure sterol:crude sterol blends can mitigate the impact of waste engine oil (e.g., REOB) on ΔTc (e.g., as assessed using 40 hour PAV aging) and renew or delay the aging rate of recycled asphalt.

[0054] The disclosed sterol blends can be used to mitigate the effects of other softeners, including synthetic or virgin lubricating oils (such as ExxonMobil Corp's MOBIL™ 1 synthetic oil and Chevron USA Inc.'s HAVOLINE™ 10W40 oil), virgin paraffinic or naphthenic base oils, untreated or unrefined waste tailings or waste engine oil materials, vacuum tower asphalt extenders (distillate fractions obtained from re-refining with engine oil), and paraffinic or naphthenic process oils.

[0055] The asphalt compositions may contain other ingredients in addition to the disclosed sterol blends, including elastomers, non-bituminous binders, adhesion promoters, softeners, revitalizers, and other suitable ingredients.

[0056] Useful elastomers include, for example, ethylene-vinyl acetate copolymers, polybutadiene, ethylene-propylene copolymers, ethylene-propylene-diene terpolymers, reactive ethylene terpolymers (e.g., ELVALOY™), butadiene-styrene block copolymers, styrene-butadiene-styrene (SBS) block terpolymers, isoprene-styrene block copolymers and styrene-isoprene-styrene (SIS) block terpolymers, chloroprene polymers (e.g., neoprene), and the like. Dry elastomer additives may be included as ground rubber materials.

[0057] Conventional revitalizers are classified into types such as RA-1, RA-5, RA-25 and RA-75 as specified in ASTM D4552. The revitalizer for use in the disclosed asphalt composition may be similar to the maltene fraction, such as, for example, RA-1 revitalizer, RA-5 revitalizer, or mixtures thereof. Examples of revitalizers include HYDROLENE™ brand asphalt oil available from Holly Frontier, KENDEX™ brand asphalt oil available from American Refining Group, or Golden Bear Preservation Products RECLAMITE™ brand asphalt oil available from Tricor Refining. Asphalt oils that meet ASTM standard D4552 and are classified as RA-1 are suitable for harder asphalts such as PG64, while RA-5, RA-25 and RA-75 oils may also be used for lower viscosity asphalts such as PG52. The rejuvenator may also include a regenerator that is rich in aromatics and resins and contains small amounts of saturates.

[0058] The disclosed asphalt compositions may be characterized according to a number of standard test methods, such as those described in the applicable ASTM specifications. For example, the disclosed compositions may be characterized using rheological tests (i.e., dynamic shear rheometer, rotational viscosity, and bending beam).

[0059] At low temperatures (e.g. -10°C), road surfaces need to be resistant to cracking; under ambient conditions, stiffness and fatigue properties are important. At elevated temperatures, roads need to resist rutting if the asphalt becomes too soft. Standards have been established by the asphalt industry to identify binder rheological properties that correlate with the performance of paved road surfaces at three common temperature conditions.

[0060] In some embodiments, the binder comprises a blend of binders. In some embodiments, the binder blend comprises a virgin binder and a binder extracted from recycled asphalt. For example, the binder extracted from RAS material may be extracted from a mixture of binders extracted from manufacturer waste asphalt shingles, consumer waste asphalt shingles, or a blend of manufacturer and consumer waste asphalt shingles. In some embodiments, the binder blend may comprise a virgin binder and a recycled binder. The virgin binder may be 60-95% by weight of the binder blend, and 2-100% by weight of recycled asphalt, such as RAS. In some embodiments, the binder blend may comprise an addition of a sterol blend from about 0.5 to about 15.0% by weight of the virgin binder. In some embodiments, the binder blend may comprise an addition of a pure sterol:crude sterol blend from about 0.2 to about 1.0% by weight of the binder. The sterol blends were shown to improve the high and low temperature properties of asphalt binder blends containing RAS, as well as the PG grades for both the high and low temperature sides.

[0061] The asphalt binder composition may be prepared by mixing or blending the pure sterol:crude sterol blend with a virgin binder to create a bituminous mixture or blend. The bituminous mixture or blend may be added to recycled asphalt (e.g., RAS and / or RAP) and aggregate. One skilled in the art will recognize that the components may be added and mixed in any order.

[0062] The asphalt composition may be prepared by applying mechanical or thermal convection. In an embodiment, a method of preparing an asphalt composition includes mixing or blending a pure sterol:crude sterol blend with virgin asphalt at a temperature of about 100°C to about 250°C. In an embodiment, the sterol blend is mixed with the virgin asphalt at a temperature of about 125°C to about 175°C, or 180°C to 205°C. In an embodiment, the asphalt composition is mixed with asphalt, a sterol blend, and a softener. In yet another embodiment, the asphalt composition is mixed with RAS, a sterol blend, and aggregate. To determine the ΔTc parameter, the 4mm DSR testing procedure and Western Research Institute data analysis as described above were used. The DSR testing procedure and methods are disclosed in International Application No. PCT / US2016 / 37077, filed June 10, 2016, International Application No. PCT / US2016 / 064950, filed December 5, 2016, and International Application No. PCT / US2016 / 064961, filed December 5, 2016, each of which is incorporated herein by reference in its entirety.

[0063] The ΔTc parameter may also be determined using the Bending Beam Rheometer (BBR) test method based on AASHTO T313 or ASTM D664. When the BBR test method is used, it is important that tests are used at a sufficient number of temperatures such that results for a stiffness failure criterion of 300 MPa and a creep or m-value failure criterion of 0.300 are obtained below the failure criterion and some results are obtained above said failure criterion. In some instances for binders with ΔTc values ​​below -5°C, this requires BBR testing at three or more test temperatures. ΔTc values ​​calculated from data that does not meet the above referenced BBR criteria requirements are not considered to be completely accurate.

[0064] Pavement surface properties and changes can be revealed in asphalt. These surface properties are determined using atomic force microscopy (AFM). See the following references: R. M. Overney, E. Meyer, J. Frommer, D. Brodbeck, R. Luthi, L.Howald, H.-J. Guntherodt, M. Fujihira, H. Takano, and Y. Gotoh, “Friction Measurements on Phase-Separated Thin Films with a Modified Atomic Force Microscope”, Nature, 1992, 359, 133-135; E. zer Muhlen and H. Niehus, “Introduction to Atomic Force Microscopy and its Application to the Study of Lipid Nanoparticles”, Chapter 7 in Particle and Surface CharacterizationMethods, RH Muller and W. Mehnert Eds, Medpharm Scientific Pub, Stuttgart, 1997; H. Takano, J. R. Kenseth, S.-S. Wong, J. C. O'Brien, MD Porter, "Chemical and Biochemical Analysis Using Scanning Force Microscopy", Chemical Reviews 1999, 99, 2845-2890.

[0065] ATF is a type of scanning microscope that exhibits high resolution, atomic and molecular level 3D imaging. ATF can be used for both morphological imaging and force measurements. Topological imaging involves scanning a cantilever / tip across the sample surface. A laser beam reflects off the back of the cantilever and the cantilever deflection is detected with a monosensitive photodiode detector. This deflection is processed by an electronic system to measure the topological height change at the sample surface.

[0066] Surface imperfections are expressed as the average roughness on the image surface, based on the average height of said roughness extending outside the surface of the sample, expressed in μm as surface roughness, and 2 With defect data expressed as a percentage of the image area (e.g., 400 μm 2 AFM can be used to measure the effect of sterol blends in asphalt compositions, and was used to measure the effect of pure sterols on asphalt compositions in the aforementioned International Applications PCT / US2016 / 37077, PCT / US2016 / 064950, and PCT / US2016 / 064961, filed December 5, 2016.

[0067] Binders for AFM can be prepared by applying small beads to a steel stub. A knife can be used to rub the beads against the surface of the stub and the resulting film can be heated to 115°C for approximately 2 minutes to smooth the film surface. AFM images can be taken at room temperature on a Bruker Dimension Icon-PT™ scanning probe microscope. Both topographical and frictional images can be taken after annealing the asphalt film at room temperature for 72 to 96 hours. An antimony-infused silicon cantilever tip AFM probe (Bruker) can be used for the measurements. Topographical images show the vertical rise and fall associated with surface features, while frictional images allow differentiation of surface materials based on elastic, adhesive properties.

[0068] In some embodiments, a method of identifying aging in an asphalt composition and retarding aging or repairing aged asphalt includes analyzing the asphalt composition for the presence or absence of surface damage, determining the asphalt as aged when minimal surface damage is detected, and adding a pure sterol:crude sterol blend and a virgin binder to the aged asphalt binder composition to reduce or retard further aging. In some embodiments, the aged asphalt composition includes recycled asphalt, softeners and revitalizers. For example, some asphalt compositions include RAS, RAP, REOB, virgin paraffinic or naphthenic base oils, untreated or unrefined waste oil or waste engine oil materials, vacuum tower asphalt extenders, paraffinic or naphthenic process oils and lubricating base oils. In some embodiments, the average roughness of the asphalt composition including the sterol blend is 1.5 to 350 μm, 3.6 to 232 μm, or 10 to 230 μm. The invention is further illustrated in the following non-limiting examples in which all parts and percentages are by weight unless otherwise indicated. EXAMPLES

[0069] Example 1 A PG64-22 based asphalt was used to investigate the effect of a blend of crude and pure sterols compared to pure sterols alone on the aging properties of binders containing REOB. Various samples were aged in PAV for 20 and 40 hours according to ASTM D65217 and by RFTO according to ASTM D2872.

[0070] The blends were made by mixing the ingredients in a one gallon container using a low shear LIGHTNIN™ mixer manufactured by SPXFlow at temperatures between 187.8°C and -204°C (370-400°F) for approximately 30 minutes.

[0071] The blend components included 92% 64-22 binder, 8% REOB, and various concentrations of sterols provided as a blend of crude sterols in the form of tall oil pitch (obtained from Union Camp) and pure sterols (obtained from MP Biomedical).

[0072] The sterols in a crude sterol feedstock such as tall oil pitch were assumed to contain approximately 15% sterols. Therefore, the following samples contain the following estimated amounts of sterols:

[0073] 1. 85% TOP + 15% pure sterols: The amount of sterols is estimated to be (0.85 x 15) + (15) = 27.7% of the total sterols. 2. 60% TOP + 40% pure sterols: The amount of sterols is estimated to be (0.60 x 15) + (40) = 49% of the total sterols. 3. 30% tall oil pitch + 70% pure sterols: The amount of sterols is derived from tall oil pitch (0.3 x 15) + the amount of sterols derived from pure sterols (70) = 74.5% of the estimated sterols. When 10% of each of the blends was added to PG64-22 containing 8% REOB, the blends would contain 2.8% sterols, 4.9% sterols, and 7.4% sterols (based on an assumption of 15% sterols in tall oil pitch).

[0074] The results are shown in Table 3 below.

[0075] [Table 3] JPEG0007680407000004.jpg38147 Figure 4 is a plot of the data for stiffness critical temperature, m-value critical temperature and ΔTc values ​​shown in Table 3. The data plotted in Figure 4 shows that blends of tall oil pitch and pure sterols improve the ΔTc value of PG64-22 with 8% REOB versus the blends without tall oil pitch and sterols. There appears to be a dose response of total sterols in the blend and a general degradation in ΔTc values ​​as the binder ages. However, the higher levels of sterols in the blend maintain acceptable ΔTc properties even after 60 hours of PAV aging.

[0076] Table 4 shows the independent effects on 20 and 40 hour PAV aging for tall oil pitch blended in asphalt, pure sterols blended in asphalt, and blends of tall oil pitch with pure sterols in their blends with PG64-22 + 8% REOB, respectively.

[0077] [Table 4] JPEG0007680407000006.jpg40147 Data from Table 4, for the 20-hour PAV residues for the 5% and 10% tall oil blends and the 2.5% pure sterol composition, the ΔTc values ​​are similar and approximately 1°C higher than the blend with 8% REOB in PG64-22 with no other additives. This indicates that the impact of these blends on the degradation of 8% REOB in the binder is small. The ΔTc data for the 20-hour PAV residues produced with a 10% dosage of tall oil + pure sterols shows results approximately 1°C higher than the tall oil only or pure sterol only blends. For the 40-hour PAV residues, the 5% and 10% tall oil blends and the 2.5% pure sterol composition show similar results, all showing ΔTc values ​​1-2°C higher than the PG64-22 + 8% REOB blend. The 5% and 7% pure sterol blends have ΔTc values ​​3.5-4.5°C higher than the PG64-22 + REOB blend. At 40 h PAV, blends of tall oil pitch and pure sterols showed similar ΔTc characteristics to pure sterols, indicating that it is possible to obtain results similar to those achieved with pure sterols by blending pure sterols with bio-oil or bio-oil pitch residues that contain lower amounts of pure sterols.

[0078] Figure 5 shows a graph of the ΔTc results for pure sterols versus the ΔTc results for blends of tall oil pitch and pure sterols with PG64-22 base binder + 8% REOB. Figure 5 shows the similarity in ΔTc behavior at 20, 40 and 60 hours PAV aging for these two sets of materials. There is no 60 hour PAV data for PG64-22 + 8% REOB. However, it is clear that the lowest dosage level of sterol has a ΔTc value at 60 hours PAV comparable to the ΔTc results for the blends without sterols at the 40 hour PAV level.

[0079] Example 2 To study the effect of pure sterol:crude sterol blends on the aging properties of the binder, RAP that had been PAV aged for 20 hours was used. The 20 hour aged RAP was aged in a Pressurized aging vessel (PAV) according to ASTM D65217. The RAP was blended with 5% bio-oil (obtained from Cargill, Minnesota (Cargill 1103)) or 5% of the pure sterol blend. Each RAP was tested prior to mixing with the various sterol blends.

[0080] The blends were prepared by mixing the ingredients in a 3 ounce tin. The tin was covered and placed in a 60°C (140°F) oven overnight to warm and mix the ingredients. After warming overnight, the samples were hand mixed and tested for high temperature stiffness properties using the 25mm DSR test procedure, and low temperature properties were determined using the 4mm DSR test procedure. The results are reported in Table 5.

[0081] [Table 5] The results in Table 5 show that bio-oil reduces the high temperature grade of RAP by 9.6°C and the low temperature PG grade by 9.8°C. The ΔTc value increased by 1.1°C or 17.5%, and the R-value decreased by only 1.53%. This indicates that the addition of softeners does little to improve the low temperature relaxation properties of the RAP binder. The addition of sterols reduced the high temperature grade by 5.9°C and the low temperature grade by 1.6°C. However, the ΔTc value increased by 3.2°C or 72.3%, while the R-value decreased by 15.35%. These comparative data indicate that the addition of sterols does more than just soften RAP.

Claims

1. 1. An asphalt binder composition comprising a virgin asphalt binder, an aged asphalt binder, or both, and a sterol blend, the sterol blend comprising a weight ratio of pure sterols to crude sterols of 10:90 to 90:10; the sterol blend is present in an amount effective to impart a less negative ΔTc value and a reduced R value to the aged asphalt binder composition as compared to a similarly aged asphalt binder without the sterol blend; The pure sterol comprises at least 85% by weight of sterol; The asphalt binder composition, wherein the crude sterols contain less than 85% by weight of sterols.

2. 10. The asphalt binder composition of claim 1, wherein the pure sterol comprises at least 95% by weight sterol.

3. 3. A method for paving roads using the asphalt binder composition of claim 1 or 2, wherein the asphalt binder composition is prepared, mixed with aggregate, applied to a base surface, and compacted.

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