US20180023259A1 - Rejuvenating compositions for asphalt applications & methods of manufacturing the same - Google Patents
Rejuvenating compositions for asphalt applications & methods of manufacturing the same Download PDFInfo
- Publication number
- US20180023259A1 US20180023259A1 US15/553,711 US201615553711A US2018023259A1 US 20180023259 A1 US20180023259 A1 US 20180023259A1 US 201615553711 A US201615553711 A US 201615553711A US 2018023259 A1 US2018023259 A1 US 2018023259A1
- Authority
- US
- United States
- Prior art keywords
- composition
- oil
- asphalt
- weight
- emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
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Images
Classifications
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2555/00—Characteristics of bituminous mixtures
- C08L2555/40—Mixtures based upon bitumen or asphalt containing functional additives
- C08L2555/60—Organic non-macromolecular ingredients, e.g. oil, fat, wax or natural dye
- C08L2555/70—Organic non-macromolecular ingredients, e.g. oil, fat, wax or natural dye from natural non-renewable resources
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2555/00—Characteristics of bituminous mixtures
- C08L2555/40—Mixtures based upon bitumen or asphalt containing functional additives
- C08L2555/80—Macromolecular constituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2555/00—Characteristics of bituminous mixtures
- C08L2555/40—Mixtures based upon bitumen or asphalt containing functional additives
- C08L2555/80—Macromolecular constituents
- C08L2555/82—Macromolecular constituents from natural renewable resources, e.g. starch, cellulose, saw dust, straw, hair or shells
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2555/00—Characteristics of bituminous mixtures
- C08L2555/40—Mixtures based upon bitumen or asphalt containing functional additives
- C08L2555/80—Macromolecular constituents
- C08L2555/84—Polymers comprising styrene, e.g., polystyrene, styrene-diene copolymers or styrene-butadiene-styrene copolymers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N25/00—Investigating or analyzing materials by the use of thermal means
- G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
- G01N25/48—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on solution, sorption, or a chemical reaction not involving combustion or catalytic oxidation
- G01N25/4846—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on solution, sorption, or a chemical reaction not involving combustion or catalytic oxidation for a motionless, e.g. solid sample
- G01N25/4866—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on solution, sorption, or a chemical reaction not involving combustion or catalytic oxidation for a motionless, e.g. solid sample by using a differential method
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/30—Adapting or protecting infrastructure or their operation in transportation, e.g. on roads, waterways or railways
Definitions
- This disclosure relates to rejuvenating compositions for asphalt applications and methods of manufacturing the same.
- Such performance enhancements may include expanding the useful temperature interval (UTI) of asphalt, rejuvenating aged asphalt, and compatibilizing the various chemical fractions in asphalt with each other as well as with other additives such as elastomeric thermoplastic polymers in asphalt.
- UMI useful temperature interval
- the rejuvenating composition comprises a polymerized oil having a polymeric distribution ranging from about 2 to about 80 wt % oligomer content and Hildebrand solubility ranging from about 6 to about 12.
- the rejuvenating composition comprises an unmodified/non-polymerized oil having a Hildebrand solubility ranging from about 6 to about 12 and a flash point ranging from about 100° C. to about 400° C.
- the rejuvenating composition comprises a modified oil having a Hildebrand solubility ranging from about 6 to about 12 and a flash point ranging from about 100° C. to about 400° C.
- FIG. 1 illustrates various oils that may be used in the rejuvenating composition and compares oligomer content against Hildebrand solubility.
- Flash Point or “Flash Point Temperature” is a measure of the minimum temperature at which a material will initially flash with a brief flame. It is measured according to the method of ASTM D-92 using a Cleveland Open Cup and is reported in degrees Celsius (° C.),
- Olemer is defined as a polymer having a number average molecular weight (Mn) larger than 1000.
- Mn number average molecular weight
- a monomer makes up everything else and includes monoacylgyclerides (MAG), diacylglycerides (DAG), triacylglycerides (TAG), and free fatty acids (FFA).
- MAG monoacylgyclerides
- DAG diacylglycerides
- TAG triacylglycerides
- FFA free fatty acids
- Performance Grade is defined as the temperature interval for which a specific asphalt product is designed. For example, an asphalt product designed to accommodate a high temperature of 64° C. and a low temperature of ⁇ 22° C. has a PG of 64-22, Performance Grade standards are set by the America Association of State Highway and Transportation Officials (AASHTO) and the American Society for Testing Materials (ASTM).
- AASHTO America Association of State Highway and Transportation Officials
- ASTM American Society for Testing Materials
- Polydispersity Index (also known as “Molecular Weight Distribution”) is the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn).
- Mw weight average molecular weight
- Mn number average molecular weight
- the polydispersity data is collected using a Gel Permeation Chromatography instrument equipped with a Waters 510 pump and a 410 differential refractometer. Samples are prepared at an approximate 2% concentration in a THF solvent. A flow rate of 1 ml/minute and a temperature of 35° C. are used. The columns consist of a Phenogel 5 micron linear/mixed Guard column, and 300 ⁇ 7.8 mm Phenogel 5 micron columns (styrene-divinylbenzene copolymer) at 50, 100, 1000, and 10000 Angstroms. Molecular weights were determined using the following standards:
- UTI “Useful Temperature Interval”
- SHRP Strategic Highway Research Program
- PG Performance Grading
- asphalt, asphalt binder, and bitumen refer to the binder phase of an asphalt pavement, roofing, coatings or other industrial applications.
- Bituminous material may refer to a blend of asphalt binder and other material such as mineral aggregate or filler.
- the binder used in this invention may be material acquired from asphalt producing refineries, flux, refinery vacuum tower bottoms, pitch, and other residues of processing of vacuum tower bottoms, as well as oxidized and aged asphalt from recycled bituminous material such as reclaimed asphalt pavement (RAP), and recycled asphalt shingles (RAS) or in the surface layer of existing pavements.
- RAP reclaimed asphalt pavement
- RAS recycled asphalt shingles
- emulsion is defined as a multiphase material in which all phases are dispersed in a continuous aqueous phase.
- the aqueous phase may be comprised of surfactants, acid, base, thickeners, and other additives.
- the dispersed phase may comprise of the polymerized oil, thermoplastic natural and synthetic polymers, waxes, asphalt, and other additives and oils, herein collectively referred to as the “oil phase”. High shear and energy is often necessary to disperse the oil phase in the aqueous phase using apparatus such as colloidal mills.
- the rejuvenating composition for asphalt applications described herein composes an oil.
- the oil in the rejuvenation composition may be a biorenewable oil (unmodified/non-polymerized), a petroleum based oil (unmodified/non-polymerized), or polymerizations or modifications thereof.
- Biorenewable oils can include oils isolated from plants, animals, and algae.
- plant-based oils may include but are not limited to soybean oil, linseed oil, canola oil, rapeseed oil, castor oil, tall oil, cottonseed oil, sunflower oil, palm oil, peanut oil, safflower oil, corn oil, corn stillage oil, lecithin (phospholipids) and combinations, distillates, derivatives, and crude streams thereof.
- animal-based oils may include but are not limited to animal fat (e.g., lard, tallow) and lecithin (phospholipids), and combinations, distillates, derivatives, and crude streams thereof.
- animal fat e.g., lard, tallow
- lecithin phospholipids
- Biorenewable oils can also include partially hydrogenated oils, oils with conjugated bonds, and bodied oils wherein a heteroatom is not introduced, for example but not limited to, diacylglycerides, monoacylglycerides, free fatty acids (and distillate streams thereof), alkyl esters of fatty acids (e.g., methyl, ethyl, propyl, and butyl esters), diol and triol esters (e.g., ethylene glycol, propylene glycol, butylene glycol, trimethylolpropane), and mixtures and derivative streams thereof.
- An example of biorenewable oils may be waste cooking oil or other used oils.
- Petroleum based oil includes a broad range of hydrocarbon-based compositions and refined petroleum products, having a variety of different chemical compositions which are obtained from recovery and refining oils of fossil based original and considered non-renewable in that it takes millions of year to generate crude starting material,
- biorenewable or petroleum based oils may be polymerized wherein polymerization is achieved through crosslinking of the fatty acid chains and/or the glyceride fraction of the tri-glyceride molecules contained in the starting oil material utilizing sulfurization, bodying, blowing, or polyol ester (for example, polyglycerol ester or a castor oil ester, or estolides) polymerization techniques to achieve a targeted oligomerization and/or Hildebrand solubility parameter.
- polyol ester for example, polyglycerol ester or a castor oil ester, or estolides
- polymerized oil versions may also be blended with straight (i.e., non-polymerized/unmodified) biorenewable or petroleum based oil or modified variations thereof.
- Modified oils can include biorenewable or petroleum based oils modified maleic anhydride, acrylic acid, hydrogen, dicyclopentadiene, a conjugation via reaction with iodine, or interesterification.
- FIG. 1 illustrates various oils that may be used in the rejuvenating composition and compares oligomer content against Hildebrand solubility
- the oil utilized in the rejuvenating compositions has a flash point, as measured using the Cleveland Open Cup method, of at least about 100° C. and no more than about 400° C.
- the flash point is between about 200° C. and about 350° C.
- the flash point is between about 220° C. and about 300° C.
- the flash point is between about 245° C. and about 275° C.
- the viscosity of the polymerized oil will vary based on the type of starting oil material, but generally ranges from about 1 cSt to about 100 cSt at 100° C.
- the polymeric distribution ranging from about 2 wt % and about 80 wt % oligomers (20 wt % to 98 wt % monomers), and more preferably between about 15 wt % to about 60 wt % oligomers (40 wt % to 85 wt % monomers), and even more preferably between about 20 wt % to about 60 wt % oligomers (40 wt % to 80 wt % monomers) is achieved.
- the polymeric distribution ranges from about 50 wt % to about 75 wt % oligomers and about 25 wt % to about 50 wt % monomers,
- the increasing usage of recycled and reclaimed bituminous materials which contain highly aged asphalt binder from sources such as reclaimed asphalt pavements (RAP) and recycled asphalt shingles (RAS) have created a necessity for “rejuvenators” capable of partially or completely restoring the rheological and fracture properties of the. aged asphalt.
- Aging of asphalt has also been shown to increase colloidal instability and phase incompatibility, by increasing the content of high molecular weight and highly polar insoluble “asphaltene” fraction which may increasingly associate.
- the use of the oils described herein are particularly useful for RAP and RAS applications.
- the oils described in this document act as a compatibilizer of the asphalt fractions, especially in aged and oxidized asphalt, resulting in a balanced and stable asphalt binder with restored performance and durability,
- the oils described herein have been shown to be capable of rejuvenating aged asphalt binder, and modify the rheological properties of the asphalt binder.
- small dosages of the oil can be used to incorporate high content of aged recycled asphalt material into pavements and other applications resulting in significant economic savings and possible reduction in the environmental impact of the pavement through reduction of use of fresh resources.
- Additional components may be added to the oil described herein, for example but not limited to thermoplastic elastomeric and plastomeric polymers, polyphosphoric acid, anti-stripping additives, warm mix additives, emulsifiers, and/or fibers.
- the oils described herein may be used to make an emulsion for use in asphalt rejuvenation applications.
- the emulsion comprises an oil phase and an aqueous phase.
- the oil phase comprises the oil described herein and may further comprise of asphalt binder and other additives and modifiers, wherein the oil is about 0.1 to 100 wt % of the oil phase.
- the aqueous phase often comprises a surfactant and may further comprise natural and synthetic polymers (such as Styrene Butadiene Rubber and latex) and/or water phase thickeners.
- the oil phase makes up about 15 to 85 wt % of the emulsion with the aqueous phase making up the remaining balance. It is understood by those skilled in the art that emulsions are sometimes further diluted with water at time of application, thus the effective oil phase content of the diluted emulsion may he reduced indefinitely.
- a method comprising applying the emulsion to the surface of an existing pavement or applying the emulsion to treat RAS or RAP and further mixing the treated RAS or RAP with virgin asphalt thereby obtaining a rejuvenated asphalt blend.
- the emulsion may also be used as part of a cold patching material, a high performance cold patch or cold mix application that contains recycled asphalt thereby obtaining treated RAS or RAP.
- the emulsion may he used for cold-in-place recycling of milled asphalt pavements or hot-in-place recycling of milled asphalt pavements.
- a charge of precipitated sulfur (mass ranges between 6.5 grams to 56.5 grams) is added to a 1 liter round bottom flask containing 650 grams of biorenewable
- the reactor is then heated to the target reaction temperature using a heating mantle, taking care not to over shoot the target temperature by more than 5° C.
- the reaction mixture is agitated using a motorized stirrer with a stir shaft and blade.
- the reaction is continuously sparged with nitrogen at 2-12 standard cubic feet per hour (SCFH).
- SCFH standard cubic feet per hour
- reaction will create foam around 110-115° C. when the sulfur melts into the oil.
- the reaction is monitored using GPC, to measure the oligomer content and distribution, and viscosity is measured at 40° C. following ASTM D445.
- the reaction is considered complete when the desired oligomer content and Polydispersity Index has been achieved.
- the reactor is then cooled to 60° C.
- a modified asphalt binder comprising:
- the modifier was blended into the asphalt after the binder had been annealed at 150° C. for 1 hour.
- the modified asphalt was used as the oil component to make a latex modified cationic rapid set emulsion.
- the oil phase was 65.0% by total weight of the emulsion.
- the aqueous phase consisted of the following components:
- incorporación of the polymerized oil in this formulation enables use of this product in rejuvenating surface applications used for pavement maintenance and preservation, especially rejuvenating scrub seal applications, and rejuvenating fog seals and sand seals. Furthermore, the emulsified solution enables use in low unheated paving applications (known as “Cold Mixes”) such as cold in place recycling, cold patch, and cold mix pavement layers.
- Cold Mixes low unheated paving applications
- Use of rapid-setting surfactant formulations, such as that used in this example enable rapid buildup of aggregate retention and traffic resistance. As a result, in ideal conditions the road can be opened to traffic within 30 minutes to an hour of the application.
- the content of polymerized oil will vary depending on the grade of the base oil and the final desired properties.
- a modified asphalt binder comprising:
- the modifier was blended into the asphalt after the binder had been annealed at 150° C. for 1 hour.
- the modified asphalt was used as the oil phase in a latex modified cationic rapid set emulsion.
- the oil phase was 65.0% by total weight of the emulsion.
- the aqueous phase consisted of the following components:
- the content of Polymerized Oil will vary depending on the grade of the base oil and the final desired properties.
- a modified asphalt binder comprising:
- the modifier was blended into the asphalt after the binder had been annealed at 150° C. for 1 hour.
- the modified asphalt was used as the oil phase in a latex modified cationic rapid set emulsion.
- the oil phase was 65.0% by total weight of the emulsion.
- the aqueous phase consisted of the following components:
- the content of Polymerized Oil will vary depending on the grade of the base oil and the final desired properties.
- a modified asphalt binder comprising:
- the modifier was blended into the asphalt after the binder had been annealed at 150° C. for 1 hour.
- the modified asphalt was used as the oil phase in a latex modified anionic rapid set emulsion.
- the oil phase was 67% by total weight of the emulsion.
- a rapid setting anionic aqueous phase, typically used for RS2-P type emulsions was utilized.
- the emulsion can be used in rapid setting applications such as chip seals, fog seals, and sand seals.
- the content of Polymerized Oil will vary depending on the grade of the base oil and the final desired properties.
- oil in water cationic emulsion was made using the polymerized oil of Example #1 as the “oil phase. “The oil phase was 50% by total weight of the emulsion.
- the aqueous phase consisted of the following components:
- This formulation is suitable for rejuvenating surface applications used for pavement maintenance and preservation, especially rejuvenating fog seals and sand seals. Furthermore, the emulsified solution enables use in low unheated paving applications (known as “Cold Mixes”) such as cold in place recycling, cold patch, and cold mix pavement layers. Use of rapid-setting surfactant formulations, such as that used in this example, enable rapid buildup of aggregate retention and traffic resistance.
- oil in water cationic emulsion was made using the following polymerized oil as the “oil phase”:
- the oil phase was 50% by total weight of the emulsion.
- the aqueous phase consisted of the following components:
- the oil phase was 50% by total weight of the emulsion.
- the aqueous phase consisted of the following components:
- oil in water cationic emulsion was made using the following polymerized oil as the “oil phase”:
- the oil phase was 50% by total weight of the emulsion.
- the aqueous phase consisted of the following components:
- oil in water cationic emulsion was made using the following polymerized oil as the “oil phase”:
- the oil phase was 50% by total weight of the emulsion.
- the surfactant phase consisted of the following components:
- This example demonstrates the use of a triethylamine (TEA) as an emulsifier, utilizing the acid functionality of the recovered corn oil (AV of approximately 30 mg KOH/g) to produce a surfactant.
- TAA triethylamine
- AV acid functionality of the recovered corn oil
- oil in water cationic emulsion was made using the following polymerized oil as the “oil phase”.
- the oil phase was 50% by total weight of the emulsion.
- a “cutback” formulation was made using Soy Methyl Ester and a polymerized oil. This product is suitable for use in low temperature and unheated paving applications (known as “Cold Mixes”) such as cold in place recycling, cold patch, and cold mix pavement layers.
- Cold Mixes unheated paving applications
- the cutback contained the following material, blended at 60° C.:
- the resulting cutback blend of the sulfurized oil had the following properties:
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WO2020146806A1 (en) * | 2019-01-10 | 2020-07-16 | Building Materials Investment Corporation | Non-asphaltic coatings, non-asphaltic roofing materials, and methods of making thereof |
US11773265B2 (en) | 2019-09-18 | 2023-10-03 | Iowa State University Research Foundation, Inc. | Biosolvents useful for improved asphalt products utilizing recycled asphalt pavement or other brittle asphalt binders such as vacuum tower bottom |
US11787945B2 (en) | 2015-02-27 | 2023-10-17 | Cargill, Incorporated | Polymerized oils and methods of manufacturing the same |
US11958974B2 (en) | 2016-02-29 | 2024-04-16 | Iowa State University Research Foundation, Inc. | Rejuvenation of vacuum tower bottoms through bio-derived materials |
US12091858B2 (en) | 2021-07-09 | 2024-09-17 | Bmic Llc | Coatings for roofing materials and related methods |
US12122917B2 (en) | 2023-09-15 | 2024-10-22 | Cargill, Incorporated | Polymerized oils and methods of manufacturing the same |
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WO2017147485A1 (en) | 2016-02-26 | 2017-08-31 | Cargill, Incorporated | Polymerized oils & methods of manufacturing the same |
AT519266B1 (de) * | 2017-04-05 | 2018-05-15 | Oesterreichische Vialit Ges M B H | Straßenbankett und Verfahren zu dessen Herstellung |
EP3609851A4 (en) | 2017-04-12 | 2021-01-27 | Cargill, Incorporated | REGENERATION OF COMPOUNDS IN HIGH PERFORMANCE ASPHALT COMPOSITIONS WITH HIGH RECYCLED CONTENT |
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