This invention involves the addition of ester bottoms to an asphalt paving composition to improve the usable temperature range (UTR). The ester bottoms are a byproduct of refining a feedstock containing all or a portion of vegetable oil or animal fat.
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6. A method of making a paving modified asphalt composition comprising adding ester bottoms to an asphalt mixture to meet a predetermined useable temperature range, wherein the ester bottoms are a byproduct of methyl ester refining.
5. A method of making a paving modified asphalt composition comprising adding ester bottoms to an asphalt mixture to increase the useable temperature range of the paving asphalt, wherein the ester bottoms are a byproduct of methyl ester refining.
1. A method of making paving a modified asphalt composition comprising:
adding 0.1 wt % to 20 50 wt % ester bottoms to an asphalt mixture wherein the ester bottoms are a byproduct of methyl ester refining; and
adding 0-20 wt % of a polymer modifier to the ester bottoms and asphalt mixture.
0. 33. A method of making a modified asphalt composition, the method comprising:
obtaining a distillation bottoms of a distilled methyl ester product that results from reaction between methanol and at least one of vegetable oil or animal fat from which glycerin is settled and removed from the methyl ester product prior to distillation, the distillation bottoms being defined as ester bottoms;
obtaining an asphalt, and
blending the ester bottoms and the asphalt to define a modified asphalt composition, the ester bottoms being between about 0.1 wt % to about 50 wt % of the modified asphalt composition and the asphalt being between about 50 wt % to about 99.9 wt % of the modified asphalt composition.
0. 17. A method of making a modified asphalt composition, the method comprising:
reacting methanol with dry oil containing one or more of a vegetable oil or an animal fat to generate reaction products, the reaction products including at least methyl ester and glycerin;
settling the glycerin from the reaction products;
removing at least a portion of the glycerin from the reaction products to leave an ester phase;
distilling the ester phase to separate purified methyl esters from ester bottoms; and
blending the ester bottoms and an asphalt-modifier with an asphalt to define a modified asphalt composition, the ester bottoms being between about 0.1 wt % to about 50 wt % of the modified asphalt composition, the asphalt-modifier being between about 0 wt % to about 20 wt % of the modified asphalt composition, and the asphalt being between about 50 wt % to about 99.9 wt % of the modified asphalt composition.
0. 22. A method of making a modified asphalt composition, the method comprising:
reacting methanol with dry oil containing one or more of a vegetable oil or an animal fat to generate reaction products, the reaction products including at least methyl ester and glycerin;
settling the glycerin from the reaction products;
removing at least a portion of the glycerin from the reaction products to leave an ester phase;
washing the ester phase with water to remove one or more of soap, methanol, catalyst or additional glycerin;
drying the washed ester phase to define dried methyl esters;
distilling the dried methyl esters to separate purified methyl esters from ester bottoms; and
blending the ester bottoms and an asphalt-modifier with an asphalt to define a modified asphalt composition, the asphalt-modifier being selected from the group consisting of a polymer, a resin, polyphosphoric acid, gilsonite, lignin, and crumb rubber.
0. 7. A method of making a modified asphalt composition, the method comprising:
reacting methanol and dry oil to generate reaction products, the reaction products including at least methyl ester and glycerin, the dry oil being an oil that is at least partially dried to remove moisture therefrom;
settling the glycerin from the reaction products;
creating a distillation feedstock that has at least a portion of the glycerin removed from the reaction products;
distilling the distillation feedstock;
recovering distillation bottoms as ester bottoms; and
adding the ester bottoms and an asphalt-modifying polymer to an asphalt to define a modified asphalt composition, the ester bottoms being between about 0.1 wt % to about 50 wt % of the modified asphalt composition, the asphalt-modifying polymer being between about 0 wt % to about 20 wt % of the modified asphalt composition, and the asphalt being between about 50 wt % to about 99.9 wt % of the modified asphalt composition.
0. 27. A method of making a modified asphalt composition that rejuvenates recycled asphalt, the method comprising:
reacting methanol and dry oil to generate reaction products, the reaction products including at least methyl ester and glycerin, the dry oil including one or more of a vegetable oil or an animal fat that has at least some moisture removed therefrom prior to reaction with the methanol;
settling the glycerin from the reaction products;
removing at least a portion of the glycerin from the reaction products to leave an ester phase;
distilling the ester phase to separate purified methyl esters from ester bottoms; and
adding the ester bottoms to recycled asphalt to define a modified asphalt composition, the recycled asphalt being obtained from a milled road surface, the ester bottoms being between about 0.1 wt % to about 50 wt % of the modified asphalt composition and the recycled asphalt being between about 50 wt % to about 99.9 wt % of the modified asphalt composition.
0. 30. A method of making a modified asphalt composition that resists moisture susceptibility, the method comprising:
reacting methanol with dry oil to generate reaction products, the reaction products including at least methyl ester and glycerin, the dry oil including one or more of a vegetable oil or an animal fat that has at least some moisture removed therefrom prior to reaction with the methanol;
settling the glycerin from the reaction products;
removing at least a portion of the glycerin from the reaction products to leave an ester phase;
washing the ester phase with water to remove one or more of soap, methanol, catalyst or additional glycerin;
drying the washed ester phase to define dried methyl esters;
distilling the dried methyl esters to separate purified methyl esters from ester bottoms; and
blending the ester bottoms and an asphalt to define a modified asphalt composition that resists cracking, the ester bottoms being between about 0.1 wt % to about 50 wt % of the modified asphalt composition and the asphalt being between about 50 wt % to about 99.9 wt % of the modified asphalt composition.
2. The method according to of
3. The method according to of
4. The method of
0. 8. The method of claim 7, wherein the reacting of the methanol and the dry oil includes reacting the methanol and the dry oil in a multistage continuous reactor and adding methoxide catalyst to one or more stages of the multistage continuous reactor.
0. 9. The method of claim 7, wherein the ester bottoms are added to the asphalt in an amount to achieve a preselected useable temperature range of the modified asphalt composition.
0. 10. The method of claim 7, wherein the ester bottoms include unsaponifiables in an amount of at least about 10% thereof.
0. 11. The method of claim 7, wherein the ester bottoms have a viscosity range of between about 10 cP and about 900 cP at 64° C.
0. 12. The method of claim 7, wherein the ester bottoms include diglycerides and triglycerides.
0. 13. The method of claim 7, wherein the asphalt includes from about 20 wt % to about 60 wt % recycled asphalt.
0. 14. The method of claim 7, wherein the asphalt-modifying polymer has one or more monomers selected from the group consisting of butadiene, styrene, vinyl acetate, ethylene, propylene, acrylate, isoprene, and acrylamide.
0. 15. The method of claim 7, wherein adding the ester bottoms to the modified asphalt composition increases useable temperature range of the modified asphalt composition.
0. 16. The method of claim 7, wherein the dry oil is derived from one or more of a vegetable oil or an animal fat.
0. 18. The method of claim 17, wherein the reading of the methanol and the dry oil includes reacting the methanol and the dry oil in a multistage continuous reactor and adding methoxide catalyst to one or more stages of the multistage continuous reactor.
0. 19. The method of claim 17, wherein the ester bottoms include unsaponifiables in an amount of at least about 10% thereof.
0. 20. The method of claim 17, wherein the ester bottoms have a viscosity range of between about 10 cP and about 900 cP at 64° C.
0. 21. The method of claim 17, wherein the asphalt includes from about 20 wt % to about 60 wt % recycled asphalt.
0. 23. The method of claim 22, wherein the modified asphalt composition includes between about 0.1 wt % to about 50 wt % of ester bottoms, between about 0 wt % to about 20 wt % of the asphalt-modifier, and between about 50 wt % to about 99.9 wt % of the asphalt.
0. 24. The method of claim 22, wherein the ester bottoms include unsaponifiables in an amount of at least about 10% thereof.
0. 25. The method of claim 22, wherein the ester bottoms have a viscosity range of between about 10 cP and about 900 cP at 64° C.
0. 26. The method of claim 22, wherein the asphalt includes from about 20 wt % to about 60 wt % recycled asphalt.
0. 28. The method of claim 27, further comprising adding an asphalt-modifying polymer to the modified asphalt composition, the asphalt-modifying polymer being between about 0 wt % to about 20 wt % of the modified asphalt composition.
0. 29. The method of claim 28, wherein the asphalt-modifying polymer is one or more of styrene butadiene, ethylene-vinyl-acetate, ethylene-methyl-acrylate, ethylene butyl acrylate, poly-propylene, atactic polypropylene, polystyrene, polyethylene, LDPE, HDPE, oxidized high density poly-propylene, poly-phosphoric acid, natural rubber, polybutadiene, epoxy resins, polyurethane resins, acrylic resins, phenolic resins, gilsonite, lignin, diblock polymers, styrene-butadiene-styrene, linear triblock polymers, radial triblock polymers. styrene-isoprene-styrene, diblocked polymers, hydrotreated styrene-butadiene-styrene, styrene ethylene butadiene styrene polymers, styrene butadiene rubber, polyacrylamide, glycidyl-containing ethylene copolymers, or crumb rubber.
0. 31. The method of claim 30, further comprising adding an asphalt-modifying polymer to the modified asphalt composition, the asphalt-modifying polymer being between about 0 wt % to about 20 wt % of the modified asphalt composition.
0. 32. The method of claim 31, wherein the asphalt-modifying polymer is selected from the group consisting of a polymer, a resin, polyphosphoric acid, gilsonite, lignin, and crumb rubber.
0. 34. The method of claim 33, further comprising blending an asphalt-modifying polymer together with the ester bottoms and the asphalt to define the modified asphalt composition, the asphalt-modifying polymer being between about 0 wt % to about 20 wt % of the modified asphalt composition.
0. 35. The method of claim 34, wherein the asphalt-modifying polymer is selected from the group consisting of a polymer, a resin, polyphosphoric acid, gilsonite, lignin, and crumb rubber.
0. 36. The method of claim 33, wherein the asphalt includes recycled asphalt that is obtained from a milled road surface.
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The present patent application is based upon and claims the benefit of provisional patent application No. 62/341,700, filed on May 26, 2016.
The invention relates to asphalt compositions and the process for the improvement of their properties. The invention further relates to a modified asphalt composition useful for a variety of applications, particularly paving asphalt and for construction materials utilizing such compositions.
The invention relates to an asphalt paving composition made with ester bottoms. The Environmental Protection Agency provides a discussion of asphalt roads at http://www.epa.gov/ttn/chief/ap42/cho4/final/c4s05.pdf which is incorporated herein by reference.
Ester bottoms are a low value by-product of vegetable oil or animal fat refining to produce methyl ester. There is little known value for ester bottoms and they are currently marketed for animal feed, lubricants, or other industrial uses at a low price point.
Asphalt materials are used in a wide variety of applications including but not limited to paving asphalt and asphalt shingles. Paving asphalt must be sufficiently durable to withstand high and low temperature extremes without undue wear, cracking or melting. Paving asphalt hardens while in service (age hardening). Age hardening is caused by an increase in viscosity of the asphalt mixture and the gradual loss of flexibility. The degree and the rate of the hardening of the paving asphalt composition or cement are factors affecting the durability of an applied surface. It is believed that the reaction of the asphalt composition with atmospheric oxygen is the principle cause of asphalt hardening in pavement. Therefore, the asphalt industry has long sought to reduce age hardening.
Some conventional refined asphalts have been found to be incapable of reacting some requirements for resistance to either low temperature thermal cracking or high temperature rutting resistance in certain climates. Modifiers such as elastomers, plasterers, chemical gellants, and chemical modifiers can be effective in improving either, or sometimes both, low temperature thermal cracking or high temperature rutting resistance. These modifiers have varying levels of effectiveness and cost.
Conventional practice to improve low temperature properties adds softer asphaltic compounds, aromatic oils, or other additives to soften or plasticize the asphalt composition. In order to reach acceptable low temperature properties, excessive amounts of soft asphaltic materials or fluxes may be required
In addition, aromatic oils used in combination with polymers can improve the rutting resistance of asphalt. However, many times, the level of polymer required to reach the desired level of rutting resistance becomes undesirable as a result of excessive cost, rendering the composition not feasible for use as a paving composition.
Asphalt compositions may be derived, as indicated from any well-known bituminous or asphaltic substance obtained from natural sources or derived from a number of sources such as, shale oil, coal tar, and the like as well as the mixtures of two or more of such materials. As indicated, paving grade asphalt compositions are preferred in the present invention. Such paving asphalt compositions are often referred to as viscosity, penetration graded, or performance graded (PG) asphalts having penetration up to 400 as measured by ASTM method D5.
As a result of the 1987 Intermodal Surface Transportation Efficiency Act (ISTEA), a $150 million research study was commissioned in which $50 million was spent towards asphalt research for improving asphalt pavements. As a product of that research which was concluded in 1992, the Strategic Highway Research Program (SHRP) produced what is now known as the Superpave Performance Graded Binder Specification in which asphaltic binders are graded or characterized according to their relative performance in resistance to rutting, shoving or deformation at high temperatures, fatigue at intermediate temperatures, and thermal cracking resistance at low temperatures. Asphalts which normally would be graded either under the penetration or viscosity specifications are now graded as PG (Performance Graded) binders. As such, their designation will be representative of their resistance at both high and low temperature, indicating their useable temperature range (UTR) as a PG AA-BB where AA=high temperature resistance in degrees Celsius and BB is low temperature cracking resistance in minus degrees Celsius, i.e., PG 64-22 would prevent rutting up to 64° C. (147° F.) and low temperature cracking to a minus 22° C. (−72° F.). Preferred asphalts are the performance graded asphalts such as PG 46-40; PG 48-34; PG 46-28, PG 52-40; PG 52-34; PG 52-28; PG 52-22, PG 58-40, PG 58-34, PG 58-28, PG PG 58-22, PG 64-40, PG 64-34, PG64-28, PG 64-22, PG 70-40, PG 70-34, PG 70-28, PG 70-22, PG 76-40, PG 76-34, PG 76-28, PG 76-22, PG 82-34, PG 82-28, or PG 82-22. The PG in the title referring to Performance Graded, the first numeric designation referring to the binders high temperature rutting or deformation resistance temperature range limit. The last numeric designation references the cracking resistance temperature limit of the binder.
Areas of high loading or slow or standing traffic as well as areas where temperature extremes can be experienced in excess of 86° C. (187° F.) between high and low temperature levels will require the use of modifiers to obtain the increased useful temperature range. As a result, it has been common to start with softer asphalts to reach low temperature properties, while adding modifiers such as polymers to achieve high temperature rutting resistance. The use of aromatic oils also aids low temperature properties. As such, extensive levels of polymer addition is required to regain high temperature properties, especially when using aromatic oils. The use of aromatic oils can solvate the polymer to a higher degree and thus require a higher level of polymer to be used to obtain the desired high temperature rutting resistance.
A common practice of softening asphalts in the industry is to add heavy vacuum gas oil (HVGO) to paving asphalt to reach the desired useable temperature range (UTR). HVGO may be added after refining or, in some applications, it is not refined out of the asphalt materials. HVGO is a valuable commodity currently selling at about $150/ton premium over the price of asphalt, depending on the market. Therefore, adding HVGO to asphalt is an undesirable fix as it increases the cost of paving asphalt.
Notwithstanding the considerable efforts previously expended to provide an improved asphalt paving composition, there remains a continued need to increase the useable temperature range and reduce the cost associated with manufacturing asphalt paving materials. The present invention addresses both of these needs.
In producing methyl esters, including biodiesel, a feed-stock containing all or a portion of vegetable oil or animal fats is reacted and refined to produce finished products. As a part of this process, a number of by-products are produced, having varying degrees of value. On the low end of the value spectrum are ester bottoms. Ester bottoms are a co-product of refining methyl ester, including biodiesel, that is not glycerin or skimmed fatty acids. Ester bottoms generally contain methyl esters, monoglycerides, diglycerides, triglycerides, sodium soaps produced from the addition of sodium methoxide (catalyst), and unsaponafiables. The unsaponafiables generally make up about 10% of the ester bottoms. Ester bottoms, as used in the preferred embodiment of this invention, have a viscosity range 10-900 cP at 64 degrees Celsius.
In the preferred embodiment, the invention involves the addition of ester bottoms to an asphalt paving composition to improve the useable temperature range (UTR). Very specifically, the ester bottoms affect the low temperature properties more significantly than the high temperature properties. Generally, the modified asphalt composition will comprise (a) about 0.1% to about 50% of ester bottoms, (b) about 0 to about 20% of a polymer modifier, (c) 50 to about 99.9% of an asphalt obtained from conventional vacuum distillation, solvent refining or naturally occurring mineral sources.
Refiners, or user producers, will often add a polymer to paving asphalt to increase the high temperature property of the paving asphalt for warmer climates. The ester bottom modified asphalt paving composition increases the useful temperature range. Therefore the amount of polymer additive required to reach a desirable higher temperature range can be reduced, thus reducing the cost of manufacturing pavement asphalt.
Another advantage of the invention is the amount of ester bottoms used to produce a desired finished product is less than the amount of HVGO (heavy vacuum gas oil), or other modifiers currently available, required to produce an equivalent amount of finished product.
A typical paving asphalt mixture comprises a mixture of components. Principal ingredients of the paving asphalt mixture are an asphalt composition or cement and aggregate or aggregate material. In such mixtures, the ratio of asphalt composition to aggregate material varies, for example, according to the aggregate material type and the nature of the asphalt composition. As used herein, the terms “asphalt composition”, “asphalt cement” or “asphalt binder” are understood to refer to any of a variety of organic materials, solid or semi-solid at room temperature, which gradually liquefy when heated, and in which the predominate constituents are naturally occurring bitumen, e.g., Trinidad Lake, or residues commonly obtained in petroleum, synthetic petroleum, or shale oil refining, or from coal tar or the like. For example, vacuum tower bottoms produced during the refining of conventional or synthetic petroleum oils is a common residue material useful as an asphalt composition. A “paving asphalt composition”, “paving asphalt cement”, or “paving asphalt binder”, accordingly is an asphalt composition or asphalt cement having characteristics which dispose the composition to use as a paving material. This is contrasted, for example, with an asphalt composition suited for use as a roofing material. “Roofing asphalts”, usually have a higher softening point, and are thus more resistant to flow from heat on roofs. The higher softening point is generally imparted by the air blowing processes by which they are commonly produced. Paving asphalt mixtures may be formed and applied in a variety of ways, as well understood by those skilled in the art. For example, the paving asphalt composition and the aggregate can be mixed and applied at elevated temperatures while in the fluid state to form the pavement or road surface. See particularly U.S. patent application Ser. No. 5,580,376 to Hayner.
Some examples of polymers used for modifying asphalts include: Styrene Butadiene (SB), ethylene-vinyl-acetate, ethylene-methyl-acrylate, ethylene butyl acrylate, poly-propylene, atactic polypropylene, polystyrene, polyethylene, LDPE, HDPE, oxidized high density poly-propylene, poly-phosphoric acid (PPA), natural rubber, polybutadiene, epoxy resins, polyurethane resins, acrylic resins, phenolic resins, gilsonite, lignin, diblock polymers, Styrene-Butadiene-Styrene (SBS), triblock polymers which may be either linear or radial, styrene-isoprene-styrene (SIS), diblocked polymers, hydrotreated SBS, Styrene Ethylene Butadiene Styrene polymers (SEBS), Styrene Butadiene Rubber (SBR), polyacrylamide, e.g., those described in U.S. Pat. No. 4,393,155; Glycidyl-containing ethylene copolymers in U.S. Pat. No. 5,331,028; or Crum Rubbers.
Asphalt is the most recycled material in the world. Milled road surfaces are reused. Many new roads are composed of 20% recycled asphalt and as high as 60% in some applications. The reclaimed asphalt is highly oxidized from years of use, and can be rejuvenated. There are rejuvenators currently on the market at a high price point. Another advantage of the invention is the ester bottoms can be used as a rejuvenator for recycled asphalt.
The ester bottom modified asphalt may have many desirable applications including but not limited to paving asphalt, asphalt emulsions, cutback asphalts, and roofing flux.
Other objects and advantages of the present invention will become apparent to those skilled in the art upon a review of the following detailed description of the preferred embodiments and the accompanying drawings.
Referring to
The ester bottoms produced in methyl ester refining are added to any suitable asphalt composition or cement, for example, industrial asphalts used for coatings, sealants, roofing materials, adhesives, and other applications. However, paving grade asphalts are used in the preferred embodiment of the invention. The asphalt feed composition will determine the amount of ester bottoms required.
Referring now to
The type of asphalt used for the present invention can vary as illustrated by
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It can be seen from
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The above detailed description of the present invention is given for explanatory purposes. It will be apparent to those skilled in the art that numerous changes and modifications can be made without departing from the scope of the invention. Accordingly, the whole of the foregoing description is to be construed in an illustrative and not a limitative sense, the scope of the invention being defined solely by the appended claims.
Jones, Steve, Brewster, Stormy, Keppers, Dennis
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