KR20170011980A - Low cost and Hi-performance Asphalt Binder Composition for Asphalt Pavement Using Residue produced during Solvent De-Asphalting Process, And Manufacturing Method thereof - Google Patents
Low cost and Hi-performance Asphalt Binder Composition for Asphalt Pavement Using Residue produced during Solvent De-Asphalting Process, And Manufacturing Method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/26—Bituminous materials, e.g. tar, pitch
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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
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/20—Recycled plastic
- C08L2207/22—Recycled asphalt
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Abstract
Description
The present invention relates to an asphalt binder composition for use in road asphalt pavement and a method of manufacturing the same. More particularly, the present invention relates to an asphalt binder composition for low-cost and long-lasting use of remnants produced through a SDA process (solvent deasphalting process or solvent deasphalting process or solvent extraction process) Asphalt binder composition for high performance asphalt pavement and a method of manufacturing the same.
The price of asphalt, which is the main material of asphalt pavement, is also rising rapidly due to the rapid increase of crude oil prices. Therefore, it is necessary to develop alternative materials for construction and maintenance of asphalt pavement and to develop new repair method. Recently, it has been actively engaged in securing and developing a low-cost heavy oil exploration well represented by Venezuelan ultra-heavy oil and Canadian oil sands bitumen. In addition, a review of measures to apply low-cost heavy oil to the refinery process operating in Korea Some are known to be in progress. As crude oil becomes heavier in order to secure energy resources in preparation for the era of high oil prices, conventional technologies can not meet the demand for petroleum and chemical raw materials, and accordingly, there is a need to develop new technologies corresponding thereto.
In developed countries such as the United States and Canada, to secure clean oil resources production technology for continuous high oil prices and heavy oil resources, and to overcome and overcome the shortcomings of conventional technologies, new hardening technologies for low- It is actively under development. However, as the hardening process for new heavy oil becomes more sophisticated, the pitch, which is the hardening by-product in the refining process, is mass-produced. Such residues are different from the general bituminous products used as construction materials in physical / And it is difficult to utilize it as a construction material. Asphalt as a bituminous material used as a construction material is generally used as a binder for an asphalt mixture to be an asphalt pavement material or as a waterproofing agent for reinforcing the waterproofing function of a structure. Therefore, durability performance including workability in the field is secured It is essential. However, since the pitch corresponding to the hardened by-product (residue) discharged at the final stage of the refining process of the heavy oil component is the state in which oil, which is a main component for providing the functionality of the asphalt, is removed, Otherwise, there is a limit to being used as a binder for an asphalt mixture alone.
In addition, domestic refiners have been focusing on the development of technologies to extract oil from crude oil using the production of DAO (De-Asphaltene Oil) by using SDA process and catalytic hydrogenation in connection with the upgrading of low-cost heavy oil. , The quality of the asphalt binder currently used in the domestic market is also decreasing. Asphalt for road pavement is required to ensure workability and workability by the oil present in the asphalt because it is not suitable for processing as well as processing in the state where oil is removed.
Korean Patent No. 10-1120509 proposes a method for improving the quality of asphalt produced through the SDA process, but there is a limitation that the object to be achieved is limited to the lowering of the penetration of asphalt.
The present invention has been developed in view of the above situation, and as the oil refining process is advanced and improved in quality, the performance of low quality asphalt, asphaltene and pitch generated in road pavement is improved to replace existing asphalt pavement material It is an object of the present invention to provide a low-cost, high-performance asphalt binder composition for asphalt pavement using residues generated through the SDA process corresponding to the hardened by-product of low-cost heavy oil and a method for manufacturing the same.
Specifically, the present invention utilizes asphalt, asphaltene, and pitch having a lower quality (less oil content) than that of a conventional asphalt paving material as a road paving material. It is a technique of improving resistance to plastic deformation and fatigue cracking, It is an object of the present invention to provide an asphalt binder composition and a method of manufacturing the same, which can extend a common life and improve resistance to moisture to prevent road pavement damage such as a porthole.
More particularly, the present invention relates to a method for manufacturing an asphalt binder composition for asphalt pavement at a low cost by using asphalt, asphaltene and pitch, which are inexpensive materials corresponding to the residue left after extracting oil (oil) And an asphalt binder composition according to the present invention.
In the present invention, in order to achieve the above-mentioned object, the present invention provides a process for producing a rubber composition, which comprises 90 to 95% by weight of residues in the SDA process, 1 to 7% by weight of a modifying additive, 0.1 to 1.0% by weight of a reinforcing agent, , 1.0 to 3.0% by weight of styrene-butadiene-styrene, 0.1 to 1.0% by weight of sulfur and 0.1 to 0.5% by weight of a vulcanization accelerator.
Also, in order to achieve the above object, the present invention provides a method for producing a polyolefin resin, which comprises melt mixing a 90 to 95% by weight of residues of the SDA process by melt mixing 1 to 7% by weight of a modifying additive and 0.1 to 1.0% Mixing the molten mixture produced by the melt mixing step with 1.0 to 3.0% by weight of SBR or SBS and further stirring; And a vulcanization step of vulcanizing the mixture by adding 0.1 to 1.0 wt% of sulfur and 0.1 to 0.5 wt% of a vulcanization accelerator to the mixture by the mixing step and the stirring and mixing step.
In the composition of the present invention and the preparation method thereof, the modified additive is a modifying additive for softening comprising at least one oil selected from the group consisting of aromatic oil, naphthenic oil, paraffin oil and white oil It may be
Further, in the composition of the present invention and the method for producing the same, the modifying additive may be a natural oil rather than an oil produced from petroleum. The vulcanization accelerator may be a thiazole vulcanization accelerator, a guanidine vulcanization accelerator , A sulfenamide-based vulcanization accelerator, and a thiuram-based vulcanization accelerator.
In the composition of the present invention and the method for producing the same, the content of the residue of the SDA process is 92% by weight, the content of the modifying additive is 4.85% by weight, and the content of the bonding reinforcing agent is 100% by weight of the entire asphalt binder composition 0.15% by weight, SBR is in a powder form, the content is 2.6% by weight, the content of sulfur is 0.3% by weight, and the content of the vulcanization accelerator is 0.1% by weight.
According to the present invention, there is provided a low-cost high-performance asphalt binder composition for asphalt which is capable of improving the plastic deformation resistance and the fatigue crack resistance by exhibiting the flexibility and elastic effect required in ordinary heated asphalt using the remnants generated through the SDA process do.
Further, according to the present invention, in addition to the most basic function of the heated asphalt pavement, the aggregate used for the asphalt mixture and the adhesion property between the residues of the SDA process are increased, and thus pavement such as a porthole that can appear in the summer rainy season and the sea ice And has improved moisture resistance to prevent breakage.
Also, according to the present invention, it is possible to improve plastic deformation and fatigue crack resistance by using high performance and high function packaging technology over existing heated asphalt mixture, thereby increasing the service life of the package, thereby preventing premature package breakage, It has an advantage that the maintenance cost can be reduced.
Further, according to the present invention, as the continuous crude oil refining process is advanced, low quality pitch or asphaltene or asphalt can be improved to exhibit improved performance over conventional asphalt, and in a low-cost heavy oil refining process in Venezuela or Canada Black Gold mines The remnants of the SDA process can be improved to exhibit the same or higher common performance as the existing heated asphalt, thereby having an economical effect of remarkably reducing the construction cost and extending the service life of the package.
In addition, according to the present invention, the viscosity of the residue of the SDA process is remarkably reduced through the modifying additive, so that the production and the application temperature can be remarkably reduced, and the workability can be increased to exhibit a more uniform packaging performance at the time of production.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description, numerous specific details are set forth, such as specific elements, which are provided to aid in an overall understanding of the present invention, and it is to be understood that the present invention may be practiced without these specific details, It will be obvious to those who have it. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.
The asphalt binder composition according to the present invention can be used as a remnant (hereinafter referred to as "residue of SDA process ") which corresponds to a hardening by-product discharged at the final stage of the refining process of low- Quot;), a modifying additive (specifically, a softening additive), and a reinforcing agent (reinforcement agent). Specifically, the asphalt binder composition according to an embodiment of the present invention comprises 90 to 95% by weight of the residue of the SDA process, 1 to 7% by weight of the modifying additive, 0.1 to 1.0% by weight of the bonding additive, 1.0 to 3.0% by weight of one or more materials selected from the group consisting of styrene-butadiene rubber (SBR) and styrene-butadiene-styrene (SBS), 0.1 to 1.0% by weight of sulfur and 0.1 to 0.5% by weight of a vulcanization accelerator do.
In the present invention, the residue of the SDA process is 90 to 95% by weight, preferably 92 to 95% by weight, more preferably 94 to 95% by weight, based on the weight of the entire asphalt binder composition. 95% by weight. If the residue content of the SDA process is less than 90% by weight, the softening point of the asphalt binder composition becomes too low, the penetration value increases, or the high temperature grade of the co-operative grade decreases, thereby failing to secure resistance to plastic deformation. On the other hand, when the residue content of the SDA process exceeds 95% by weight, the viscosity of the asphalt binder composition increases and the asphalt paving operation becomes impossible, and cracks may be caused in the asphalt pavement due to the high hardness.
As a residue of the SDA process used in the present invention, the pitch should have an invasion degree of 30 or lower, a softening point of 50 or higher, a high temperature grade of 64 to 94 degrees Celsius and a low temperature grade of 0 degrees Celsius. The heated asphalt commonly used in the prior art has a penetration of 60 to 80, a softening point of less than 50, a high temperature grade of 58 to 64 degrees Celsius in the commonality grade, and a low temperature grade of -16 to -22 degrees Celsius in the commonality grade, The pitch used in the present invention is a completely different material from such conventional heated asphalt.
Conventional asphalt binder compositions for use in asphalt road pavement comprise about 4-6 wt.% Of saturates, about 50-60 wt.% Aromatics, about 20-21 wt.% Of resins, asphaltene) of about 19 to 25% by weight. However, the residues produced through the SDA process contain about 1 to 3.5% by weight of a seturate, about 50 to 60% by weight of aromatics, about 19 to 22% by weight of resins, about 22 to 23% by weight of asphaltene, , And thus shows a large difference in the content of the settler. Due to the difference in the content of such a detergent, the residues of the SDA process have a very hard characteristic and are therefore excellent in resistance against deformation which can be generated at a high temperature. However, such rigid properties of the residues of the SDA process ultimately lead to very brittle characteristics, which are disadvantageous in that crack resistance caused by winter or vehicle load is remarkably low.
As described above, the residues of the SDA process have a lower brittle characteristic because the content of the surfactant is lower than that of conventional asphalt binders. Therefore, in the present invention, flexibility is secured by softening the properties of brittleness by adding a modifying additive. Specifically, in the present invention, a modifying additive is used to improve the remnants of the SDA process to soft asphalt. Among the chemical components constituting the remnants of the SDA process, the settler, which is relatively insufficient as compared with the conventional asphalt binder composition, is chemically reinforced Or the residual components of the SDA process can not be filled with relatively less chemical components as compared with the conventional asphalt binder composition, but the physical properties of the residues of the SDA process can be compared with conventional asphalt binder compositions And a modifying additive to be the same as the composition was selected and used.
Specifically, as the modifying additive contained in the asphalt binder composition according to the present invention, the "modifying additive for softening ", which can chemically reinforce the settler, comprises an aromatic oil, naphthenic oil, paraffin oil and white oil ≪ / RTI > The components constituting the oil are generally composed of three components: an aromatic component having a benzene ring in a molecular structure, a naphthenic component having a cyclic structure, and a paraffinic component having a linear structure do. Among the above three components, "aromatic oil" is referred to as having a large amount of aromatic components, "naphthenic oil" as having a large amount of naphthenic components, and "paraffin oil" as having many paraffin components. On the other hand, a transparent oil that does not contain an aromatic component and has no color is called "white oil ".
As described above, in the present invention, the residual components of the SDA process can not be filled with relatively less chemical components than the conventional asphalt binder composition, but the physical properties of the residues of the SDA process are the same as those of the conventional asphalt binder composition In this case, "natural oil" rather than oil produced from petroleum is used as a modifying additive. Natural oils can be classified into vegetable oils and animal oils. The vegetable oils include soybean oil, castor oil, palm oil, rapeseed oil, sunflower oil, oil, and corn oil. Examples of animal oils include fish oil and pig oil. In general, vegetable oil has a structure in which three fatty acids are bound to a glycerol junction at a triglyceride molecule, and free fatty acids, stearin, pigment components and fat soluble vitamins .
In the present invention, one of the above-mentioned vegetable oil and animal oil can be used as a modifying additive. In order to improve the adhesion between asphalt and asphalt and the adhesion between aggregate and asphalt, a natural oil having a polar group is selected, Is preferably used.
The asphalt binder composition according to the present invention contains 1 to 7% by weight of a modifier for softening, which is made of petroleum-derived oil or petroleum-derived natural or vegetable oil, and the preferred content of the modifying additive Is 3 to 6% by weight, and the content of the modifying additive is more preferably 3 to 5% by weight. If the content of the modifying additive is less than 1% by weight, the brittle characteristics of the asphalt mixture containing the asphalt binder composition become strong, and when the asphalt mixture is produced, the asphalt mixture can not be produced due to viscosity increase, The production of the asphalt mixture must be induced. In addition, since the brittle characteristics of the asphalt mixture are strong, resistance to temperature cracks such as occurrence of shrinkage cracks as the temperature is lowered is reduced, and second infiltration damage is caused by moisture penetration, Thereby causing fatigue crack failure. Therefore, the content of the modifying additive should be 1% by weight or more. On the other hand, if the content of the modifying additive exceeds 7% by weight, the rigidity of the residue of the SDA process is reduced, and the deformation due to the traffic load at the high temperature in the summer is greatly generated, . Therefore, the content of the modifying additive should be 7 wt% or less.
The asphalt binder composition according to the present invention contains 0.1 to 1.0% by weight, preferably 0.1 to 0.5% by weight, more preferably 0.1 to 0.3% by weight, based on the total weight of the asphalt binder composition. If the content of the bonding reinforcing agent is less than 0.1% by weight, the aggregating material and the asphalt or the asphalt and the asphalt can not exhibit the effect of increasing the bonding force and the adhesion force, and they can not serve as surfactants, . When the content of the bonding reinforcing agent exceeds 1.0% by weight, the bonding property with the natural oil contained as the modifying additive may be reduced, phase separation may occur, and the economical efficiency may be reduced.
As the bonding reinforcing agent, an amine-based or silane-based material can be used, and the bonding reinforcing agent improves the moisture sensitivity of the asphalt binder composition and enhances the peeling prevention function. The amine-based or silane-based materials have a moiety capable of strongly bonding to the aggregate in the molecular structure, and also have a portion that exhibits strong affinity with the residues of the SDA process. Therefore, when an amine-based or silane-based material is contained as a bonding reinforcing agent, it exhibits a strong affinity with each material constituting the asphalt mixture, and consequently exhibits an effect of strengthening the adhesive strength. Also, the amine-based or silane-based material as the bonding reinforcing agent is mixed with the asphalt to serve as a surfactant, thereby reducing the contact angle when the asphalt is in contact with the aggregate. This is because when the asphalt is wetted The effect of improving the properties is exhibited. Considering economical efficiency, it is more preferable to use an amine-based material as a bonding additive rather than a silane-based material. The amine-based bonding agent used in one embodiment of the present invention has a total amine number of 461.17 to 462.45 mg HClO 4 / g, and has a specific gravity of 0.90 to 0.95 and a viscosity Is preferably 400 to 2,000 cPs. If the viscosity of the amine-based bonding reinforcing agent is less than 400 cPs, the material separation may occur during mixing. Conversely, if the viscosity exceeds 2,000 cPs, the mixing and workability may be reduced.
The asphalt binder composition according to the present invention contains SBR (Styrene-Butadiene Rubber) and SBS (Styrene-Butadiene-Styrene) alone or as a mixture thereof in an amount of 1.0 to 3.0% by weight. SBR and SBS can be used in powder form. If the content of SBR and SBS is less than 1 wt%, the asphalt modifying effect and sufficient adhesion with asphalt pavement material can not be expected. On the other hand, when the content selected from SBR and SBS exceeds 3% by weight, mixing with asphalt may be impossible due to excessive viscosity increase. In dividing the asphalt grade (PG) One level rise. Therefore, in the present invention, the content selected from SBR and SBS is 3% by weight or less.
In one embodiment of the present invention, the powdered SBR may have a molecular weight ranging from 300,000 to 1,000,000. When the molecular weight of the powdery SBR is less than 300,000, it may be difficult for the powders to be homogeneously dispersed when put into the asphalt. If the molecular weight of the powdery SBR exceeds 1,000,000, the powder is not dispersed in the asphalt under the condition, It may not be usable. In particular, in one embodiment of the present invention, the powdered SBR may have a particle size of greater than 0 mm and less than 1 mm. When the particle size of the powdery SBR is more than 1 mm, the time to disperse into the asphalt is delayed, and gel phenomenon due to chemical bonding between the molecules may occur before dispersing, so that dispersion into the asphalt may become impossible.
In another embodiment of the asphalt binder composition according to the present invention, CRM (Crumb Rubber Modifier / Waste Tire Powder Asphalt Modifier), SBS (Styrene-Butadiene-Styrene) block copolymer, LDPE one or two selected from the group consisting of high density polyethylene (HDPE), polypropylene, ethyl vinyl acetate (EVA), ethylene acralate copolymer, The above auxiliary additives may be used. In the present invention, the auxiliary additive may be contained in an amount of 0.5 to 1.5 parts by weight based on 100 parts by weight of the total binder composition.
The above-mentioned auxiliary additives are added to improve watertightness, adhesion, tensile strength and elongation of the asphalt mixture. CRM, which can be used as an auxiliary additive, is obtained by crushing waste tire, and preferably has a particle diameter of 0.08 to 2.00 mm. If the particle size of the CRM is less than 0.08 mm, it is difficult to grind and the inefficiency such as cost increase occurs. If the particle size is more than 2.0 mm, it is difficult to achieve sufficient mixing as the reforming agent. Therefore, the particle diameter of the CRM is preferably 0.08 to 2.0 mm, but is not limited thereto.
Meanwhile, low density polyethylene (HDPE), high density polyethylene (HDPE), polypropylene, and ethylene acralate copolymer may be used as an auxiliary additive to replace SBR or SBS. These become auxiliary additives for increasing the stiffness of the asphalt mixture, i.e., resistance to deformation. A material with a melting point of 150 ° C or less is used, which is very commonly used in the field of ethylene resins.
The sulfur used in the present invention can serve to enhance the high temperature plastic deformation of the asphalt, such as the increase of the softening point, and it is possible to use a general sulfur having a melting point of 110 to 120 degrees and a solid powder state at room temperature. In one embodiment of the asphalt binder composition according to the present invention, the sulfur may be contained in an amount of 0.1 to 1.0 wt%, preferably 0.1 to 0.5 wt%, more preferably 0.1 to 0.3 wt%, based on the total weight of the asphalt binder composition. If the content of sulfur is less than 0.1 wt%, the vulcanization effect of SBR or the like is insufficient, so there is no effect of improving the high temperature performance of the asphalt such as softening point. If it exceeds 1.0 wt%, the asphalt becomes gelled due to excessive vulcanization, have.
In one embodiment of the present invention, the sulfur may be in a powder state having a particle diameter of more than 0 mm but not more than 0.3 mm. When the diameter of the sulfur powder is more than 0.3 mm, the SBR dispersed in the asphalt is not uniformly vulcanized and phase separation phenomenon may occur and it may be difficult to obtain a uniform quality of the binder.
In one embodiment of the asphalt binder composition according to the present invention, the vulcanization accelerator is selected from the group consisting of a thiazole vulcanization accelerator, a guanidine vulcanization accelerator, a sulfenamide vulcanization accelerator, and a thiuram vulcanization accelerator And the like. In one embodiment of the present invention, the vulcanization accelerator may be included in an amount of 0.1 to 0.5% by weight, preferably 0.1 to 0.4% by weight, more preferably 0.1 to 0.3% by weight, based on the total weight of the asphalt binder composition. If the content of the vulcanization accelerator is less than 0.1% by weight, the effect of promoting vulcanization may not be exhibited. If the content of the vulcanization accelerator is more than 0.5% by weight, further improvement of the vulcanization accelerating effect may not be achieved.
In the method of the present invention for producing the asphalt binder composition of the present invention described above, a step of melt mixing (mixing) 90 to 95% by weight of the residue of the SDA process with 1 to 7% by weight of the modifying additive and 0.1 to 1.0% (Mixing and mixing step), and further adding 1.0 to 3.0% by weight of SBR or SBS to the mixture by stirring (stirring mixing step), and vulcanizing by adding 0.1 to 1.0% by weight of sulfur and 0.1 to 0.5% by weight of a vulcanization accelerator Step).
In the melt mixing step of melt-mixing the modifying additive and the bonding reinforcing agent in the residue of the SDA process, the modifying additive and the bonding reinforcing agent may be premixed in advance, and then the mixture may be melt-mixed into the residue of the SDA process. In particular, in the melt mixing step of melt-mixing the modifying additive and the bonding reinforcing agent into the residues of the SDA process, it is preferable to heat the residues of the SDA process to secure sufficient fluidity of the asphalt binder composition. Specifically, Deg.] C, preferably about 180 [deg.] C. When the temperature at the time of melt mixing is less than 160 ° C, sufficient fluidity can not be secured with respect to the residues of the SDA process. Therefore, when the asphalt binder composition is mixed with the aggregate, smooth mixing can not be expected and the aggregate covering by the asphalt binder composition There is a problem that is not completely accomplished. On the other hand, if the temperature during the melt mixing exceeds 200 degrees Celsius, rapid oxidation and curing of the residues of the SDA process may occur and the resistance to cracks may be reduced, leading to early breakage of road pavement such as cracks.
In the melt mixing step, the molten mixture of the modifying additive and the bonding additive and the residue of the SDA process may be formed by adding the modifying additive and the bonding reinforcing agent to the remnants of the molten SDA process, as described above, but the modifying additive and the bonding adjuvant Is preliminarily mixed at a temperature of 20 to 60 ° C., and a mixture of the modifying additive and the bonding reinforcing agent is added to the residue of the molten SDA process and stirred to obtain a molten mixture of the modifying additive and the bonding additive and the residue of the SDA process . And further stirring for 10 to 30 minutes in the melt mixing step. In this case, it is preferable that the additional stirring process is performed at a temperature of 160 to 180 degrees Celsius for easy control of the temperature.
In the stirring and mixing step subsequent to the melt mixing step, the powdery SBR or the powdery SBS can be uniformly dispersed in the molten mixture composed of the modifying additive and the bonding reinforcing agent and the residue of the SDA process. Of course, SBR and SBS may be added together and mixed by stirring. Such a stirring mixing step may be performed at a temperature of 160 to 200 degrees Celsius, preferably 170 to 180 degrees Celsius. The performance of the residue of the SDA process in which the temperature of the stirring and mixing step exceeds 200 degrees Celsius and the performance of SBR or SBS.
The stirring mixing step may also be carried out for 30 to 60 minutes. If the mixing time is less than 30 minutes, SBR or SBS may not be sufficiently mixed and it may be difficult to obtain a uniform dispersed phase. If the mixing time exceeds 60 minutes, the SDA process residue and degradation due to aging of SBR or SBS may result .
In the vulcanization step, the vulcanization step is carried out by adding sulfur and a vulcanization accelerator to the mixture obtained through the previous step and stirring the mixture. This vulcanization step can be carried out at a temperature of 150 to 200 degrees Celsius. When the temperature in the vulcanization step is less than 150 ° C., the flowability of the molten mixture is not ensured and it is difficult for the SBR or SBS to be uniformly dispersed in the mixture. On the other hand, if the temperature of the vulcanizing step exceeds 200 ° C, the performance degradation may occur due to aging of SBR or SBS. The vulcanization step can be carried out for 30 to 60 minutes. When the vulcanization time is less than 30 minutes, the vulcanization of SBR or SBS does not sufficiently proceed and sufficient reforming effect can not be obtained. If the vulcanization time exceeds 60 minutes, the degradation of the SDA process residue and the degradation of SBR or SBS .
Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are illustrative of the present invention, and the scope of the present invention is not limited to the following examples.
(1) Preparation of Examples and Comparative Examples According to the Present Invention
In order to prepare an embodiment of the asphalt binder composition according to the present invention, residues of the SDA process were first melted by heating at about 180 degrees Celsius and stirred with a stirrer. The modifying additive and the bonding reinforcing agent were gradually added to the residue of the SDA process being stirred, and stirring was continued. The modifying additive and the bonding reinforcing agent were added, and the modifying additive and the bonding reinforcing agent were completely melted and mixed with the residue while stirring for about 10 to 20 minutes. The temperature of the mixture is inevitably raised at the time of stirring, and therefore, the additional heating is preferably performed at 200 DEG C or less for easy control of the temperature.
Powdered SBR or SBS was added to the molten mixture of the remnants of the SDA process, the modifying additive and the bonding reinforcing agent, and the mixture was stirred for 30 minutes to 60 minutes to ensure homogeneous dispersibility. Stirring after the addition of SBR or SBS is preferably carried out at a temperature of 200 DEG C or lower, specifically in the range of 170 DEG C to 180 DEG C.
The vulcanization process was completed by adding sulfur and a vulcanization accelerator to the thus-formed mixture and stirring at a temperature of 150 to 200 degrees Celsius for 30 minutes to 60 minutes to prepare an asphalt binder composition according to the present invention.
(2) Property evaluation method for the examples and comparative examples according to the present invention
In the examples of the asphalt binder composition according to the present invention manufactured through the above process, penetration and softening point measurement tests were performed to evaluate the basic properties of the composition, and shrinkage tests And bending beam rheometer tests were performed, and the kinematic viscosity was measured. The asphalt binder composition according to the embodiment of the present invention may also be used in the form of a binder such as DSR (Dynamic Shear Rheometer), BBR (Bending Beam Rheometer), RTFO (Rolling Thin Film Oven), and PAV (Pressure Aging Vessel) Grade) were measured.
Intrusion measurement tests are carried out to determine the degree of hardness and to determine the degree of penetration for embodiments of asphalt binder compositions without short-term aging (RTFO) and long-term aging (PAV). The test is performed at 25 ° C immersed in water. The test is performed for 2 hours or more before the test. The depth of the test needle (needle) is measured for 5 seconds using a weight of 100 g.
The softening point measurement test measures the temperature at which the asphalt is softened by heat. Asphalt is heated at a rate of 5 degrees Celsius per minute while measuring the temperature at which the iron ball climbs on the asphalt.
The Bending Beam Rheometer test is performed on samples subjected to short-term aging and long-term aging, where short-term aging ages the asphalt binder through Rolling Thin Film Oven (RTFO) Simulates the asphalt aging of the mix production and construction phases.
Long-term aging produces samples through Pressure Aging Vessel (PAV), which ages the samples after a short-term aging test. Long-term aging simulates the aging of asphalt pavements with a public age of about 5 to 10 years.
In addition, the Bending Beam Rheometer test is a test to measure the temperature crack resistance in the low temperature region. Conventional tests on asphalt binders have measured physical properties in a limited range, such as 25 degrees Celsius and 60 degrees Celsius. However, the asphalt pavement which is in common use is affected not only by the high temperature and the intermediate temperature but also by the low temperature condition below the freezing point, and the asphalt is very hard so that the behavior is similar to the elastic body. The deflection holding motive was developed based on the beam theory to evaluate the characteristics of asphalt under these low temperature conditions, and the main purpose is to provide reference materials for physical hardening of asphalt. The specimens are fabricated from samples that have undergone aging for a short period of time and then aged again.
In actual tests, creep loads (constant loads) were applied to asphalt specimens in the form of beams under the lowest temperature conditions under which the packages would be experienced for a period of 240 seconds and creep stiffness (resistance to creep load) St) and the stiffness change rate (m-value).
The performance grade (PG grade) of asphalt is classified into high temperature grade and low temperature grade. Dynamic grade rheometer test is used to determine the high temperature grade and the low temperature grade is determined through the deflection holding motive. Generally, as the high temperature grade goes up, the low temperature grade decreases, and as the low temperature grade goes up, the high temperature grade decreases. Conventionally used asphalt has a PG grade of <hot grade: 64 / low grade: 16> or <high grade: 64 / low grade: 22>.
Tests were conducted on the asphalt binder composition according to the present invention by applying the test method described above.
(3) According to the present invention In the embodiment Test results for
1) < Examples 1 to 6 >
Modified remover, powdered SBR (LG Chem, product name: SBR1502) or SBS (KKPC, product name: SBS3102), sulfur (Taikyu Chemical Co., Examples of the asphalt binder composition according to the present invention were prepared by the above-described production method using sulfur powder (product name: sulfur powder) and vulcanization accelerator (KUMHO Petrochemical, product name: KUMAC D).
2) < Comparative Examples 1 to 4 >
The asphalt binder composition of the present invention was prepared according to the preparation method described above using only the residues of the SDA process, the modifying additives and the bonding adjuvant according to the composition ratios set forth in Table 1 below.
3) < Comparative Example 5 >
Comparative Example 5, which was made of only a straight asphalt binder (product name: AP5, manufactured by SK Corporation), was evaluated for physical properties in the same manner as in the examples of the present invention, and the test results are shown in Table 2 below.
4) < Comparative Example 6 >
As summarized in Table 2, the composition consisting of only the residue of the SDA process was used as Comparative Example 6, and the properties were evaluated in the same manner as in the Examples of the present invention, and the test results are shown in Table 2 below.
Experimental results on Examples 1 to 6 show that the viscosity of the composition containing SBS as a whole is increased and the viscosity and BBR stiffness of the composition containing SBR are increased. It was also found that the higher the SBR or SBR content, the higher the performance at high temperature. In the case of low temperature, it satisfied all the criteria even at minus 12 degrees Celsius.
As shown in Table 1, when the SBR or SBS is contained in an amount of 1 wt% or more, the performance at high temperature is improved. If the SBR or SBS is contained in an amount exceeding 3 wt%, the BBR Stiffness becomes 300 MPa or more Therefore, it was found that the standard of 300 MPa or less was not satisfied. It was also found that the addition of more than 3% by weight of SBS did not satisfy the standard of 3,000 cP or less even at a viscosity of 135 ° C.
Therefore, it was confirmed that the addition of the modifying additive reduced the brittleness property and maintained the high temperature performance as SBR or SBS was added. The low temperature grade was also minus 22 degrees Celsius and the same grade as the existing high performance asphalt binder. Through this, it can be applied to the section where deformation is likely to occur due to the high temperature in summer, and it can be applied to the section where cracks and temperature cracks occur.
Claims (7)
1 to 7% by weight of a modifying additive;
0.1 to 1.0% by weight of a bonding reinforcing agent;
1.0 to 3.0% by weight of one or more materials selected from the group consisting of SBR and SBS;
0.1 to 1.0% by weight of sulfur; And
And 0.1 to 0.5% by weight of a vulcanization accelerator, based on the total weight of the asphalt binder composition.
Wherein the modifying additive is a modifying additive for softening comprising one or more oils selected from the group consisting of aromatic oil, naphthenic oil, paraffin oil and white oil.
The asphalt binder composition for asphalt paving, characterized in that the modifying additive is a natural oil, not an oil produced from petroleum.
Wherein the vulcanization accelerator is at least one selected from the group consisting of a thiazole vulcanization accelerator, a guanidine vulcanization accelerator, a sulfenamide vulcanization accelerator, and a thiuram vulcanization accelerator Asphalt binder composition for asphalt pavement.
The content of the SDA process residue is 91.6% by weight, the content of the modifying additive is 4.85% by weight, the content of the bonding reinforcing agent is 0.15% by weight, and the content of the SBR is in the form of powder, based on 100% by weight of the entire asphalt binder composition. 3% by weight, the sulfur content is 0.3% by weight, and the content of the vulcanization accelerator is 0.1% by weight.
The content of the SDA process residue was 91.6% by weight, the content of the modifying additive was 4.85% by weight, the content of the bonding reinforcing agent was 0.15% by weight, the content of SBS was 3% by weight based on 100% by weight of the entire asphalt binder composition , The sulfur content is 0.3 wt%, and the content of the vulcanization accelerator is 0.1 wt%.
Further comprising 1.0 to 3.0% by weight of at least one material selected from the group consisting of SBR and SBS to the molten mixture produced by the melt mixing step, followed by stirring and mixing; And
And vulcanizing the vulcanization step by adding 0.1 to 1.0 wt% of sulfur and 0.1 to 0.5 wt% of a vulcanization accelerator to the mixture by the stirring and mixing step.
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| KR102034561B1 (en) * | 2019-04-03 | 2019-10-21 | 한국석유공업 주식회사 | Modified asphalt composition and pavement of bridge using the same |
| KR102425968B1 (en) * | 2021-07-16 | 2022-07-28 | 오영훈 | Eco-friendly modified asphalt and a process for the preparation thereof |
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