CN115491046B - Modified asphalt with long-acting self-cleaning function, cleaning modifier and preparation method - Google Patents
Modified asphalt with long-acting self-cleaning function, cleaning modifier and preparation method Download PDFInfo
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Abstract
The invention provides modified asphalt with a long-acting self-cleaning function, a cleaning modifier and a preparation method thereof, wherein the modified asphalt is prepared from the following raw materials: road asphalt, cleaning modifier, dispersant and coupling agent. The cleaning modifier is prepared from the following raw materials: tourmaline powder, biochar and diatomite mixture and cupric oxide ore powder. The cleaning modifier has a multistage pore structure, a piezoelectricity effect and high thermal conductivity, the multistage pore structure can effectively adsorb harmful substances in asphalt smoke and automobile exhaust, the permanent spontaneous polarization effect of the cleaning modifier further reduces and degrades pollutants in the asphalt smoke and the automobile exhaust, tourmaline powder, biochar, diatomite mixture and chalcocite powder jointly improve the cleaning effect of the self-cleaning modified asphalt, and the full life cycle self-cleaning effect of asphalt pavement is enhanced.
Description
Technical Field
The invention belongs to the technical field of road materials, relates to modified asphalt, and in particular relates to modified asphalt with a long-acting self-cleaning function, a cleaning modifier and a preparation method thereof.
Background
At present, the road construction in China mainly takes asphalt pavement as a main material, and a series of technical problems in ecological environment protection still exist in the construction and operation processes of the asphalt pavement at the present stage, such as: the hot-mix asphalt mixture in the construction stage produces a great deal of smoke to pollute the environment, the volatile harmful substances of the asphalt pavement in the operation stage, the emission of the road area automobile exhaust to pollute the atmosphere and the like. In order to reduce pollutant discharge amount of the hot-mix asphalt mixture, research on partial hot-mix emission reduction modified asphalt and a mixture technology is carried out at home and abroad, and the emission reduction principle is that a functional modifier is added into asphalt to inhibit release of asphalt smoke harmful substances under high temperature conditions, and the emission reduction effect is mainly concentrated in the construction stages of mixture mixing, paving and the like, but does not relate to emission reduction of volatile harmful substances in the operation period and the maintenance period of an asphalt pavement, so that the aim of self-cleaning of asphalt pavement pollutants is difficult to truly realize; in addition, ecological environmental protection problems such as emission of road area automobile exhaust pollutants should also be brought into the clean scope of asphalt pavement.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide modified asphalt with a long-acting self-cleaning function, a cleaning modifier and a preparation method thereof, and solves the technical problem that the long-acting effectiveness of the self-cleaning function of the existing modified asphalt is to be further improved.
In order to solve the technical problems, the invention adopts the following technical scheme:
a modified asphalt with a long-acting self-cleaning function is prepared from the following raw materials: road asphalt, cleaning modifier, dispersant and coupling agent.
The cleaning modifier is prepared from the following raw materials: tourmaline powder, biochar and diatomite mixture and cupric oxide ore powder.
The pore diameter of the biochar is distributed between 7.5 and 110nm, the pore diameter of the diatomite is distributed between 0.23 and 0.8 mu m, the particle size of tourmaline powder is 1.2 to 3.0 mu m, the Mohs hardness is 7.5, the particle size of the chalcocite powder is 0.11 to 0.27 mu m, and the Mohs hardness is 2.
The invention also has the following technical characteristics:
specifically, in the cleaning modifier, the mass ratio of tourmaline powder, biochar and diatomite mixture to the chalcocite powder is 2:1:0.3.
preferably, in the mixture of the biochar and the diatomite, the mass ratio of the biochar to the diatomite is 1:1.
Specifically, the material is prepared from the following raw materials in parts by weight: 74-84 parts of road asphalt, 10-20 parts of cleaning modifier, 2 parts of dispersing agent, 4 parts of coupling agent and 100 parts of raw material by mass.
Preferably, the material is prepared from the following raw materials in parts by weight: 79 parts of road asphalt, 15 parts of cleaning modifier, 2 parts of dispersant and 4 parts of coupling agent.
Preferably, the road asphalt is 70# matrix asphalt, 90# matrix asphalt, SBS modified asphalt or rubber powder modified asphalt.
Preferably, the dispersing agent is laureth, fatty alcohol polyalkoxy ether or isomeric trideceth.
Preferably, the coupling agent is a silane coupling agent or a phthalate coupling agent.
The invention also provides a preparation method of the modified asphalt with the long-acting self-cleaning function, which comprises the following steps:
step one, pretreatment of raw materials of a cleaning modifier:
adding the isomeric tridecanol polyoxyethylene ether into the deionized water solution of tourmaline powder, reacting for 12 hours at room temperature, stirring every 1 hour, filtering the powder of the tourmaline powder after the reaction is finished, drying in a 60 oven, sieving and storing for later use.
The biochar is placed in a mixed solution of N- (2-hydroxyethyl) ethylenediamine and 30wt.% NaOH, stirred at normal temperature, left to stand for 2 hours, filtered out, sieved and stored for later use.
Soaking diatomite in 1, 6-hexanediol diacrylate, heating to 400 ℃, pyrolyzing and carbonizing the diatomite, filtering out the diatomite, sieving and storing the diatomite for later use.
Adding fatty alcohol polyalkoxyl ether into the solution of the cupric ore powder and deionized water, reacting for 12 hours at room temperature, stirring every 1 hour, filtering out powder after the reaction is finished, drying in a baking oven at 60 ℃, sieving and storing for later use.
Step two, preparing a cleaning modifier:
step 201, respectively weighing tourmaline powder, biochar, diatomite and chalcocite powder pretreated in the step one according to the mass ratio, placing the biochar and the diatomite into 10wt.% ammonia water solution, dropwise adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide, performing ultrasonic dispersion for 20min, and then adding the tourmaline powder and the chalcocite powder and uniformly stirring to form a biochar/diatomite/tourmaline powder/chalcocite powder solution.
And 202, placing the biochar/diatomite/tourmaline powder/chalcocite powder solution into a planetary high-energy ball mill, wherein the ball milling speed is 200rpm, the ball milling time is 2 hours, and completing the ball milling process to obtain the cleaning modifier solution.
And 203, taking out the ball-milled cleaning modifier solution, placing the ball-milled cleaning modifier solution in a 180 ℃ oven for drying to constant weight, taking out the dried solid product, and grinding, sieving and dispersing the solid product to obtain the cleaning modifier.
Step three, preparing self-cleaning modified asphalt:
heating road asphalt to 150+/-5 ℃, slowly adding a cleaning modifier and a silane coupling agent into the road asphalt, firstly stirring at a low speed by using a stirrer for 10min, shearing at a shearing rate of 800-1200 rpm, shearing at a high speed by using a shearing machine for 30min, shearing at a shearing rate of 3000-3500 rpm, and manually stirring until bubbles in the modified asphalt disappear, thereby obtaining the modified asphalt with a long-acting self-cleaning function.
The invention also protects a cleaning modifier which is prepared from the following raw materials: tourmaline powder, biochar and diatomite mixture and cupric oxide ore powder.
The pore diameter of the biochar is distributed between 7.5 and 110nm, the pore diameter of the diatomite is distributed between 0.23 and 0.8 mu m, the particle size of tourmaline powder is 1.2 to 3.0 mu m, the Mohs hardness is 7.5, the particle size of the chalcocite powder is 0.11 to 0.27 mu m, and the Mohs hardness is 2.
In the cleaning modifier, the mass ratio of tourmaline powder, biochar and diatomite mixture to the cupric oxide mineral powder is 2:1:0.3.
in the mixture of the biochar and the diatomite, the mass ratio of the biochar to the diatomite is 1:1.
The invention also provides a preparation method of the cleaning modifier, which comprises the step one and the step two.
Compared with the prior art, the invention has the following technical effects:
the cleaning modifier has a multi-stage pore diameter structure, a piezoelectricity effect and high thermal conductivity, the multi-stage pore diameter structure can effectively adsorb harmful substances in asphalt smoke and automobile exhaust, the permanent spontaneous polarization effect of the cleaning modifier further reduces and degrades pollutants in the asphalt smoke and the automobile exhaust, tourmaline powder, biochar, diatomite mixture and chalcocite powder jointly improve the cleaning effect of the self-cleaning modified asphalt, and the full life cycle self-cleaning effect of asphalt pavement is enhanced.
(II) in the cleaning modifier of the invention, tourmaline powder has the function of adsorbing and degrading harmful substances of asphalt smoke through spontaneous polarization effect.
(III) in the cleaning modifier of the present invention, the mixture of biochar and diatomaceous earth acts to adsorb harmful substances in asphaltic smoke.
In the cleaning modifier, chalcocite powder has two functions, wherein the first function is to serve as a spontaneous polarization effect auxiliary agent of tourmaline powder, and the chalcocite powder has excellent heat and electric conductivity and is used for enhancing the spontaneous polarization effect of the tourmaline powder. The second function of the cupric ore powder is a pore size regulator which is used for regulating the pore size distribution of the mixture of the biochar and the diatomite; the pore diameter of the mixture of the biochar and the diatomite is too large or too small to influence the adsorption effect on the asphalt smoke, the pore diameter distribution of the mixture of the biochar and the diatomite is regulated through the synergy between the cupric ore powder and the biochar and the diatomite, the adsorption saturation effect of the mixture of the biochar and the diatomite can be reduced to the greatest extent, and the adsorption effect on the asphalt smoke is improved.
The self-cleaning modified asphalt solves the environmental problems of low emission reduction rate, high emission reduction rate and high emission of automobile exhaust in the construction period, the operation period, the maintenance period and the like of the existing asphalt pavement, and realizes the effects of high-quality long-acting emission reduction and road area automobile exhaust purification of the asphalt pavement in the whole life cycle of the construction period, the operation period, the maintenance period and the like.
The self-cleaning modified asphalt of the invention can clean pollutants on asphalt pavement and greatly improve the key road performances of asphalt such as high temperature, low temperature and aging resistance.
In the present invention, the dispersant is used to disperse the cleaning modifier and the coupling agent is used to improve the compatibility of the cleaning modifier with road asphalt.
(VIII) the modified asphalt with the long-acting self-cleaning function, which is developed by the invention, can reduce the release of harmful substances of an asphalt pavement in a construction stage, an operation stage and a maintenance stage, reduce the emission of automobile exhaust in a road area, realize the automatic cleaning of the asphalt pavement in the whole life cycle, and relieve the pressure of the service and ecological environment of the road.
Drawings
Fig. 1 (a) is an SEM micrograph of diatomaceous earth in a cleaning modifier.
FIG. 1 (b) is an SEM micro-morphology of biochar in a cleaning modifier.
Fig. 2 (a) is an isothermal adsorption desorption curve in BET analysis of the cleaning modifier.
FIG. 2 (b) is an adsorption dV (log) curve in BET analysis of the cleaning modifier.
FIG. 3 (a) is a penetration and softening point diagram in examples 1 to 3.
Fig. 3 (b) is a ductility graph in examples 1 to 3.
Fig. 4 (a) is a graph comparing the penetration before and after aging of example 2 and comparative examples 7 to 9.
Fig. 4 (b) is a graph comparing softening points before and after aging of example 2 and comparative examples 7 to 9.
Fig. 4 (c) is a graph comparing the before and after aging ductility of example 2 with those of comparative examples 7 to 9.
FIG. 5 (a) is a graph of complex modulus aging index after heat-curing aging of example 2 and comparative examples 7 to 9.
FIG. 5 (b) is a graph of the complex modulus aging index after UV aging of example 2 and comparative examples 7 to 9.
Fig. 6 is a graph of the emission reduction rate of the self-cleaning asphalt of examples 1 to 3.
Fig. 7 is a graph showing the effect of reducing emissions of the modified asphalt of example 2 and comparative examples 1 to 6.
Fig. 8 is a graph of the exhaust gas purification rates of examples 1 to 3.
Fig. 9 is a graph showing the exhaust gas purification rates of example 2 and comparative examples 1 to 6.
The following examples illustrate the invention in further detail.
Detailed Description
All the raw materials used in the present invention are those commonly known in the art, unless otherwise specified. The SBS modified asphalt or the rubber powder modified asphalt is commonly known.
The road asphalt is 70# matrix asphalt, 90# matrix asphalt, SBS modified asphalt or rubber powder modified asphalt.
The dispersing agent is laurinol polyoxyethylene ether, fatty alcohol polyalkoxy ether or isomeric tridecanol polyoxyethylene ether.
The coupling agent is a silane coupling agent or a phthalate coupling agent.
The following specific embodiments of the present invention are provided, and it should be noted that the present invention is not limited to the following specific embodiments, and all equivalent changes made on the basis of the technical solutions of the present application fall within the protection scope of the present invention.
Example 1:
the embodiment provides modified asphalt with a long-acting self-cleaning function, which is prepared from the following raw materials in parts by mass: 84 parts of road asphalt, 10 parts of cleaning modifier, 2 parts of dispersant and 4 parts of coupling agent.
The selection and specification of the raw materials in this example were the same as in example 2.
The pore size, particle diameter and hardness of the cleaning modifier raw material of this example were the same as those of example 2.
The preparation method of the modified asphalt with the long-acting self-cleaning function in this example is the same as that in example 2.
Example 2:
the embodiment provides modified asphalt with a long-acting self-cleaning function, which is prepared from the following raw materials in parts by mass: 79 parts of road asphalt, 15 parts of cleaning modifier, 2 parts of dispersant and 4 parts of coupling agent.
The cleaning modifier is prepared from the following raw materials: the mass ratio of tourmaline powder, biochar and diatomite mixture to the cupric oxide ore powder is 2:1:0.3;
in the mixture of the biochar and the diatomite, the mass ratio of the biochar to the diatomite is 1:1.
In the embodiment, the pore diameter of the biochar is distributed between 7.5 and 110nm, the pore diameter of the diatomite is distributed between 0.23 and 0.8 mu m, the particle size of tourmaline powder is 1.2 to 3.0 mu m, the Mohs hardness is 7.5, the particle size of the copper-back ore powder is 0.11 to 0.27 mu m, and the Mohs hardness is 2.
The road asphalt is 70# matrix asphalt.
The dispersing agent is isomeric tridecanol polyoxyethylene ether.
The coupling agent is a silane coupling agent.
The preparation method of the modified asphalt with the long-acting self-cleaning function comprises the following steps:
step one, pretreatment of raw materials of a cleaning modifier:
adding isomeric tridecanol polyoxyethylene ether into deionized water solution of tourmaline powder, reacting for 12 hours at room temperature, stirring every 1 hour, filtering powder of tourmaline powder after the reaction is finished, drying in a 60 oven, sieving and storing for later use;
placing biochar in a mixed solution of N- (2-hydroxyethyl) ethylenediamine and 30wt.% NaOH, stirring at normal temperature, standing for 2h, filtering, sieving, and storing for use;
soaking diatomite in 1, 6-hexanediol diacrylate, heating to 400 ℃, pyrolyzing and carbonizing the diatomite, filtering out the diatomite, sieving and storing the diatomite for later use;
adding fatty alcohol polyalkoxyl ether into the solution of the copper powder and deionized water, reacting for 12 hours at room temperature, stirring every 1 hour, filtering out powder after the reaction is finished, drying in a baking oven at 60 ℃, sieving and storing for later use;
step two, preparing a cleaning modifier:
step 201, respectively weighing tourmaline powder, biochar, diatomite and chalcocite powder pretreated in the step one according to the mass ratio, placing the biochar and the diatomite into 10wt.% ammonia water solution, dropwise adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide, performing ultrasonic dispersion for 20min, then adding tourmaline powder and chalcocite powder, and uniformly stirring to form a biochar/diatomite/tourmaline powder/chalcocite powder solution;
step 202, placing biochar/diatomite/tourmaline powder/chalcocite powder solution into a planetary high-energy ball mill, wherein the ball milling speed is 200rpm, the ball milling time is 2 hours, and completing the ball milling process to obtain a cleaning modifier solution;
and 203, taking out the ball-milled cleaning modifier solution, placing the ball-milled cleaning modifier solution in a 180 ℃ oven for drying to constant weight, taking out the dried solid product, and grinding, sieving and dispersing the solid product to obtain the cleaning modifier.
Step three, preparing self-cleaning modified asphalt:
heating road asphalt to 150+/-5 ℃, slowly adding a cleaning modifier and a silane coupling agent into the road asphalt, firstly stirring at a low speed by using a stirrer for 10min, shearing at a shearing rate of 800-1200 rpm, shearing at a high speed by using a shearing machine for 30min, shearing at a shearing rate of 3000-3500 rpm, and manually stirring until bubbles in the modified asphalt disappear, thereby obtaining the modified asphalt with a long-acting self-cleaning function.
The asphalt smoke component contains a plurality of harmful substances in a complex way, and the dynamic diameter distribution range of different harmful substances molecules is wide (between nanometer and micrometer). The pore diameter of the mixture of the biochar and the diatomite is too large or too small to influence the adsorption effect on the asphalt smoke, and the adsorption saturation problem exists in the adsorption process. If the cleaning modifier has an effective adsorption effect on asphalt smoke harmful substances, the cleaning modifier is required to contain a micro-meso-macroporous multilevel pore structure, and based on the cleaning modifier, the cleaning efficiency of the self-cleaning modified asphalt is improved by adjusting the pore size distribution of the cleaning modifier to be matched with the particle size of the asphalt smoke harmful substances.
The pore diameter of the biochar is distributed between 7.5 and 110nm, the pore diameter of the diatomite is distributed between 0.23 and 0.8 mu m, the particle size of tourmaline powder is 1.2 to 3.0 mu m, the Mohs hardness is 7.5, the particle size of the cupric oxide ore powder is 0.11 to 0.27 mu m, and the Mohs hardness is 2. The particle size of tourmaline powder is far higher than the aperture of biochar and is generally larger than the aperture of diatomite, so that the particle size of the powder is not suitable for diatomite pore filling, while the chalcocite powder used in the method has small particle size, the particle size of the powder is positioned in a diatomite aperture distribution area, the particle size of the powder can be directly used for diatomite pore filling, in addition, the hardness of the powder is only 2, and after ball milling, part of the powder is ground into fine fragments and can be used for biochar pore filling, therefore, the method adopts the chalcocite powder as an aperture regulator to adjust the pore structures of biochar and diatomite, and further prepares multi-level aperture powder.
To determine whether the cleaning modifier prepared by the invention has a target pore size structure, SEM is adopted to characterize the microstructure of the pore structure of the cleaning modifier, and the BET is used to verify the multistage pore size distribution characteristics of the cleaning modifier, and the test results are shown in fig. 1 (a) to 2 (b).
As can be seen from FIG. 1 (a), after ball milling, tourmaline powder and biochar are uniformly covered on the surface of diatomite in the cleaning modifier, the diatomite disc has a rich pore structure, no blocking phenomenon exists, the pore diameter of the large pores is generally reduced, part of the large pores in the disc grow into mesopores, and the analysis proves that the cupric ore powder is wrapped with a small amount of tourmaline powder and is attached to the wall of the diatomite hole together, so that the pore structure is adjusted, and the diatomite contains mesopores and the large pore structure.
As can be seen from fig. 1 (b), the surface pore structure of the biochar in the cleaning modifier is uniform and compact, because the chalcocite powder has low hardness, part of the chalcocite powder is worn into fine scraps under the action of long-time ball milling, the lost pore structure on the biochar is filled, and the new compact mesoporous structure is formed by stacking, and at the moment, the biochar contains mesoporous and microporous structures.
As can be seen from fig. 2 (a), the adsorption amount of the cleaning modifier isotherm prepared by the present invention increases suddenly in the low pressure region, and single-layer adsorption occurs, which indicates that the composite powder contains a microporous structure; an H4 type hysteresis loop appears in the medium pressure area, and the curve is an IV type adsorption-desorption curve, which shows that the cleaning modifier contains a large amount of mesoporous structures; no plateau appears in the high-pressure area and the adsorption quantity rises rapidly, which indicates that the cleaning modifier contains a part of macroporous structure.
As is clear from FIG. 2 (b), the cleaning modifier contains a large amount of mesoporous structure, and the pore size distribution is mainly concentrated in 2.3-34.8 nm, and the most probable pore size is 4.4nm and 32nm.
As can be seen from fig. 1 (a) to fig. 2 (b), the cleaning modifier contains a micro-meso-macro multi-level pore structure, and the content of the mesoporous structure is the largest, so that the target pore structure is achieved, and the self-cleaning modified asphalt cleaning effect is improved.
Example 3:
the embodiment provides modified asphalt with a long-acting self-cleaning function, which is prepared from the following raw materials in parts by mass: 74 parts of road asphalt, 20 parts of cleaning modifier, 2 parts of dispersant and 4 parts of coupling agent.
The selection and specification of the raw materials in this example were the same as in example 2.
The pore size, particle diameter and hardness of the cleaning modifier raw material of this example were the same as those of example 2.
The preparation method of the modified asphalt with the long-acting self-cleaning function in this example is the same as that in example 2.
Comparative example 1:
this comparative example gives a modified asphalt differing from example 2 only in that 15 parts of the cleaning modifier of example 2 was replaced by 15 parts of the tourmaline powder alone in equal amounts.
The modified asphalt of this comparative example was prepared in substantially the same manner as in example 2.
Comparative example 2:
this comparative example gives a modified asphalt differing from example 2 only in that 15 parts of cleaning modifier in example 2 was replaced by 15 parts of biochar alone in equal amounts.
The modified asphalt of this comparative example was prepared in substantially the same manner as in example 2.
Comparative example 3:
this comparative example gives a modified asphalt differing from example 2 only in that 15 parts of the cleaning modifier of example 2 was replaced in this comparative example by 15 parts of the chalcocite powder alone in equal amounts.
The modified asphalt of this comparative example was prepared in substantially the same manner as in example 2.
Comparative example 4:
this comparative example gives a modified asphalt differing from example 2 only in that 15 parts of the cleaning modifier in example 2 was replaced with 10 parts of tourmaline powder, 2.5 parts of biochar and 2.5 parts of diatomaceous earth in equal amounts.
The modified asphalt of this comparative example was prepared in substantially the same manner as in example 2.
Comparative example 5:
this comparative example gives a modified asphalt differing from example 2 only in that 15 parts of cleaning modifier in example 2 was replaced in this comparative example by 15 parts of pyrophyllite in equal amounts.
The modified asphalt of the comparative example is prepared by uniformly stirring pyrophyllite in heated asphalt.
Comparative example 6:
this comparative example gives a modified asphalt differing from example 2 only in that 15 parts of the cleaning modifier in example 2 were replaced with 8 parts of zinc borate and 7 parts of magnesium hydroxide in equal amounts.
The preparation method of the modified asphalt of the comparative example is to put magnesium hydroxide and zinc borate into heated asphalt and stir uniformly.
Comparative example 7:
the comparative example shows an asphalt, namely 70# asphalt, which is obtained by using a commercially available product.
Comparative example 8:
the comparative example shows an asphalt, namely SBS asphalt, which is obtained by using commercial products.
Comparative example 9:
the comparative example shows an asphalt, namely SBR modified asphalt, which is obtained by adopting a commercial product.
Performance test:
the performance test of the self-cleaning modified asphalt comprises three parts, namely a basic performance test, an emission reduction effect test and a purification effect test of the self-cleaning modified asphalt, and according to the test rules of highway engineering asphalt and asphalt mixture (JTGE 20-2011), three indexes and a complex modulus aging index of the self-cleaning modified asphalt are measured, so that the change rule of the road performance of the self-cleaning modified asphalt is defined; and testing the total life cycle harmful substance emission of the asphalt pavement, calculating the asphalt smoke emission reduction rate and the automobile exhaust purification rate of the asphalt pavement in the construction period, the operation period and the maintenance period, and verifying the environmental effects of self-cleaning modified asphalt, such as emission reduction, purification and the like.
(1) Basic performance:
as can be seen from fig. 3 (a) to fig. 4 (c), the basic road performances of penetration, ductility, softening point and the like of the self-cleaning modified asphalt all meet the related technical requirements of the technical Specification for construction of highway asphalt pavement (JTG F40-2004), and can be used in the road field.
Compared with matrix asphalt, the self-cleaning modified asphalt has the advantages of increased softening point and increased ductility, and the self-cleaning modified asphalt has higher and lower temperature performance than the matrix asphalt.
Compared with the comparative examples, the example 2 has higher penetration residual ratio and smaller softening point increment after aging by a film oven and ultraviolet, and has the minimum ductility reduction after aging, and the three indexes of the self-cleaning modified asphalt have small amplitude after aging, which indicates that the self-cleaning modified asphalt can ensure the long-term stability of high and low temperature performance of the asphalt pavement in the operation period more than the matrix asphalt, SBS modified asphalt and SBR modified asphalt.
As can be seen from fig. 5 (a) and fig. 5 (b), the SBS, SBR and the cleaning modifier can improve the aging resistance of asphalt, wherein the complex modulus aging index after heat curing and ultraviolet aging in example 2 is the lowest, and the aging resistance is the best, because the cleaning modifier composed of tourmaline powder, biochar, diatomite mixture and chalcocite powder in the present invention can isolate ultraviolet rays and has a certain anti-oxidation aging capability. Example 2 has an increase in uv aging resistance of about 72% and an increase in heat aging resistance of about 53%, indicating that the cleaning modifier has an increase in uv aging resistance of asphalt that is superior to the increase in heat aging resistance.
(2) Emission reduction efficacy:
the temperature interval of the asphalt pavement in the construction period is 160-180 ℃ and the temperature interval of the asphalt pavement in the operation period is 50-70 ℃, and in order to comprehensively evaluate the emission reduction effect of the self-cleaning modified asphalt in the whole life cycle, the emission reduction efficiency of the asphalt pavement in the construction period and the emission reduction efficiency of the asphalt pavement in the operation period are respectively evaluated by adopting the emission reduction rate of the asphalt mixture at 170 ℃ and 60 ℃; in addition, the emission reduction effect of the asphalt pavement in the maintenance period comprises two parts: and the heat emission reduction effect of the mixture in the construction period and the operation period of the regenerated asphalt pavement. Therefore, the self-cleaning modified asphalt mixture after aging is tested for the emission reduction rate at 170 ℃ and 60 ℃ and used for evaluating the emission reduction effect of the asphalt pavement in the maintenance stage, the calculation method of the emission reduction rate of the asphalt mixture in different stages is shown in a formula I, and the test results are shown in fig. 6 and 7.
Wherein:
e is the asphalt smoke emission reduction rate of the self-cleaning modified asphalt mixture at different stages.
c 0 The asphalt smoke emission concentration of the common hot-mix asphalt mixture at different stages is achieved.
c 1 The asphalt smoke emission concentration of the self-cleaning modified asphalt mixture at different stages is achieved.
As can be seen from FIG. 6, in examples 1 to 3, the emission reduction rate of the asphalt pavement in the construction period is 50.76 to 60.54%, the emission reduction rate of the asphalt pavement in the operation period is 47.51 to 57.62%, the emission reduction rate of the regenerated asphalt pavement in the construction period is 46.38 to 56.21%, the emission reduction rate of the regenerated asphalt pavement in the operation period is 44.21 to 54.43%, the emission reduction rate of each pollutant emission stage is more than 42%, excellent emission reduction effects are shown, the attenuation degree of the produced self-cleaning asphalt with the reduction rate along with the passage of the life cycle of the road is small, and the example 3 with the maximum reduction of the emission reduction rate is only 7.26%, which shows that the long-acting emission reduction effects of the self-cleaning modified asphalt prepared by the invention are obvious in the whole life cycle.
Comparative examples 1 to 3, example 2 was the best in terms of asphalt smoke emission reduction rate in the whole life cycle of asphalt pavement, wherein the asphalt pavement was 60.54% in terms of construction period emission reduction rate, 57.62% in terms of asphalt pavement operation period emission reduction rate, 56.21% in terms of construction period emission reduction rate, 54.43% in terms of regenerated asphalt pavement operation period emission reduction rate, and the best in terms of emission reduction efficiency. Therefore, the mixing amount of the cleaning modifier is preferably 16.5%, and the mass ratio of tourmaline powder, biochar and diatomite mixture to the chalcocite powder is 2:1: example 2 of 0.3 is the best example for emission reduction efficacy.
As shown in fig. 7, the emission reduction rate of comparative example 1 in each pollutant emission stage is significantly reduced compared with that of example 2, the emission reduction rate of comparative example 2 is significantly reduced along with the passage of the life cycle of the road, the emission reduction rate of the regenerated asphalt pavement in the operation period is only 12.37%, and the emission reduction rate of comparative example 3 is within 1%, because tourmaline powder is used as an emission reduction agent, asphalt smoke can be adsorbed only by means of a micro electric field around the tourmaline powder, biochar is used as an emission reduction agent, the biochar is saturated along with the adsorption progress, so that the emission reduction effect of asphalt smoke is suddenly reduced, and the cupric powder is used as an emission reduction agent, and the asphalt smoke has no adsorption and degradation functions. Therefore, the modified asphalt prepared by adopting the single tourmaline powder, the mixture of the biochar and the diatomite or the cupric oxide ore powder as the emission reducing agent has poor emission reducing effect.
In the comparative example 4, tourmaline powder, biochar and diatomite mixture are adopted for composite modification, the emission reduction efficiency is obviously improved compared with that of single material modification, but the emission reduction rate is only 20.01-35.68%, the emission reduction rate still has larger attenuation in the life cycle, and in the example 2, the emission reduction rate is improved by 23.32-27.32% compared with that in the comparative example 4, and no obvious attenuation exists in the life cycle of the pavement. The invention adopts tourmaline powder, biochar, diatomite mixture and chalcocite powder as cleaning modifier, on one hand, the chalcocite powder greatly enhances spontaneous polarization effect of the tourmaline powder, on the other hand, the pore size distribution of the diatomite and the biochar is regulated, the adsorption saturation state of the diatomite and the biochar is improved, and meanwhile, the degradation effect of tourmaline on asphalt harmful substances is improved, and the tourmaline powder, the biochar, the diatomite mixture and the chalcocite powder synergistically enhance the cleaning effect of the self-cleaning modified asphalt.
In the embodiment 2, the emission reduction rate of asphalt smoke in each pollutant emission stage is within 54.32-60.13%, the emission reduction rate in each stage is obviously improved compared with the current hot-mix emission reduction asphalt comparative examples 5 and 6, the emission reduction efficiency is excellent, the emission reduction rate of asphalt smoke does not obviously attenuate along with the passage of the life cycle of a road, the attenuation is only 5.56% in the life cycle, and the emission reduction efficiency shows obvious long-acting characteristics, so that the invention combines tourmaline powder, biochar, diatomite and chalcocite powder as cleaning modifiers, realizes the synergistic emission reduction of the tourmaline powder, the biochar, diatomite mixture and the chalcocite mineral powder, has obvious emission reduction efficiency, and solves the problems that the asphalt pavement operation period and the asphalt smoke emission reduction in the maintenance period are not realized by the current hot-mix emission reduction asphalt.
(3) Purifying effect:
the purification effect refers to the purification of CO in automobile exhaust in the operation period of asphalt pavement X HC and NO X And the absorption and degradation effects of main gas pollutants, and in order to determine the self-cleaning modified asphalt purifying effect developed by the invention, the tail gas concentration before and after absorption and degradation of the self-cleaning modified asphalt mixture is measured, the purifying rate is calculated according to a formula II, and the test results are shown in figures 8 and 9.
Wherein:
t is the automobile exhaust purification rate.
f 0 Is the initial emission concentration of the automobile exhaust.
f 1 The concentration of the automobile tail gas after being absorbed and degraded by the self-cleaning modified asphalt mixture.
As can be seen from FIG. 8, the tail gas purifying rate of each example is 44.67-48.08%, the tail gas purifying efficiency is excellent, wherein the tail gas purifying rate of example 2 is the highest and 48.08%, the tail gas purifying efficiency is the best, the self-cleaning asphalt tail gas purifying rate of the examples is 2 & gt 1 & gt 3 according to the order of magnitude, and the self-cleaning asphalt tail gas purifying rate is the same as the asphalt smoke emission reduction powerThe effect shows a consistent rule, because the automobile exhaust gas component is the same as the asphalt smoke component, the modified asphalt with the long-acting self-cleaning function of the invention degrades CO in the exhaust gas component through negative oxygen ion absorption X HC and NO X The tail gas purification is realized, and the tail gas purification mechanism is similar to the asphalt smoke emission reduction mechanism.
As can be seen from fig. 9, comparative example 3 is chalcocite powder modified asphalt, comparative examples 5 and 6 are the current hot mix emission reduction asphalt, and neither of them has the tail gas purifying effect, and the tail gas purifying rates of comparative examples 1 and 2 are 23.32% and 10.21%, respectively, which indicates that the single tourmaline powder or biochar modified asphalt has a certain tail gas purifying effect, and comparative example 4 has a tail gas purifying rate of 39.21%, which indicates that the compound modified asphalt of the tourmaline powder, the biochar and the diatomite has a better tail gas purifying effect than that of the compound modified asphalt of the single material, and the optimal tail gas purifying rate of example 2 is 48.08%, which is 8.87% higher than that of comparative example 4.
Claims (7)
1. The modified asphalt with the long-acting self-cleaning function is characterized by being prepared from the following raw materials: road asphalt, a cleaning modifier, a dispersing agent and a coupling agent;
the cleaning modifier is prepared from the following raw materials: tourmaline powder, biochar and diatomite mixture and chalcocite powder;
the pore diameter of the biochar is distributed between 7.5 and 110 and nm, the pore diameter of the diatomite is distributed between 0.23 and 0.8 mu m, the particle size of tourmaline powder is 1.2 to 3.0 mu m, the Mohs hardness is 7.5, the particle size of the chalcocite powder is 0.11 to 0.27 mu m, and the Mohs hardness is 2;
in the cleaning modifier, the mass ratio of tourmaline powder, biochar and diatomite mixture to the cupric oxide mineral powder is 2:1:0.3;
in the mixture of the biochar and the diatomite, the mass ratio of the biochar to the diatomite is 1:1.
2. The modified asphalt with the long-acting self-cleaning function as claimed in claim 1, which is characterized by being prepared from the following raw materials in parts by weight: 74-84 parts of road asphalt, 10-20 parts of cleaning modifier, 2 parts of dispersing agent, 4 parts of coupling agent and 100 parts of raw material by mass.
3. The modified asphalt with the long-acting self-cleaning function as claimed in claim 2, which is characterized by being prepared from the following raw materials in parts by weight: 79 parts of road asphalt, 15 parts of cleaning modifier, 2 parts of dispersant and 4 parts of coupling agent.
4. The modified asphalt with the long-acting self-cleaning function according to claim 1, wherein the road asphalt is 70# matrix asphalt, 90# matrix asphalt, SBS modified asphalt or rubber powder modified asphalt;
the dispersing agent is fatty alcohol polyalkoxyl ether;
the coupling agent is a silane coupling agent or a phthalate coupling agent.
5. A method for producing a modified asphalt having a long-lasting self-cleaning function according to any one of claims 1 to 4, comprising the steps of:
step one, pretreatment of raw materials of a cleaning modifier:
adding isomeric tridecanol polyoxyethylene ether into deionized water solution of tourmaline powder, reacting at room temperature for 12h, stirring every 1h, filtering powder of tourmaline powder after the reaction is completed, drying in a 60 oven, sieving, and storing for later use;
placing biochar in a mixed solution of N- (2-hydroxyethyl) ethylenediamine and 30wt.% NaOH, stirring at normal temperature, standing for 2h, filtering, sieving, and storing for use;
soaking diatomite in 1, 6-hexanediol diacrylate, heating to 400 ℃, pyrolyzing and carbonizing the diatomite, filtering out the diatomite, sieving and storing the diatomite for later use;
adding fatty alcohol polyalkoxyl ether into the solution of the copper powder and deionized water, reacting at room temperature for 12h, stirring every 1h, filtering out powder after the reaction is finished, drying in a baking oven at 60 ℃, sieving and storing for later use;
step two, preparing a cleaning modifier:
step 201, respectively weighing tourmaline powder, biochar, diatomite and chalcocite powder pretreated in the step one according to the mass ratio, placing the biochar and the diatomite into 10wt.% ammonia water solution, dropwise adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide, performing ultrasonic dispersion for 20min, then adding tourmaline powder and chalcocite powder, and uniformly stirring to form a biochar/diatomite/tourmaline powder/chalcocite powder solution;
step 202, placing biochar/diatomite/tourmaline powder/chalcocite powder solution into a planetary high-energy ball mill, wherein the ball milling speed is 200rpm, the ball milling time is 2h, and completing a ball milling process to obtain a cleaning modifier solution;
step 203, taking out the ball-milled cleaning modifier solution, placing the ball-milled cleaning modifier solution in a 180 ℃ oven for drying to constant weight, taking out the dried solid product, and grinding, sieving and dispersing to obtain the cleaning modifier;
step three, preparing self-cleaning modified asphalt:
heating road asphalt to 150+/-5 ℃, slowly adding a cleaning modifier and a silane coupling agent into the road asphalt, firstly stirring at a low speed by using a stirrer for 10min, shearing at a shearing rate of 800-1200 rpm, shearing at a high speed by using a shearing machine for 30min, shearing at a shearing rate of 3000-3500 rpm, and manually stirring until bubbles in the modified asphalt disappear, thereby obtaining the modified asphalt with a long-acting self-cleaning function.
6. The cleaning modifier is characterized by being prepared from the following raw materials: tourmaline powder, biochar and diatomite mixture and chalcocite powder;
the pore diameter of the biochar is distributed between 7.5 and 110 and nm, the pore diameter of the diatomite is distributed between 0.23 and 0.8 mu m, the particle size of tourmaline powder is 1.2 to 3.0 mu m, the Mohs hardness is 7.5, the particle size of the chalcocite powder is 0.11 to 0.27 mu m, and the Mohs hardness is 2;
in the cleaning modifier, the mass ratio of tourmaline powder, biochar and diatomite mixture to the cupric oxide mineral powder is 2:1:0.3;
in the mixture of the biochar and the diatomite, the mass ratio of the biochar to the diatomite is 1:1.
7. A method of preparing the cleaning modifier of claim 6, comprising the steps of:
step one, pretreatment of raw materials of a cleaning modifier:
adding isomeric tridecanol polyoxyethylene ether into deionized water solution of tourmaline powder, reacting at room temperature for 12h, stirring every 1h, filtering powder of tourmaline powder after the reaction is completed, drying in a 60 oven, sieving, and storing for later use;
placing biochar in a mixed solution of N- (2-hydroxyethyl) ethylenediamine and 30wt.% NaOH, stirring at normal temperature, standing for 2h, filtering, sieving, and storing for use;
soaking diatomite in 1, 6-hexanediol diacrylate, heating to 400 ℃, pyrolyzing and carbonizing the diatomite, filtering out the diatomite, sieving and storing the diatomite for later use;
adding fatty alcohol polyalkoxyl ether into the solution of the copper powder and deionized water, reacting at room temperature for 12h, stirring every 1h, filtering out powder after the reaction is finished, drying in a baking oven at 60 ℃, sieving and storing for later use;
step two, preparing a cleaning modifier:
step 201, respectively weighing tourmaline powder, biochar, diatomite and chalcocite powder pretreated in the step one according to the mass ratio, placing the biochar and the diatomite into 10wt.% ammonia water solution, dropwise adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide, performing ultrasonic dispersion for 20min, then adding tourmaline powder and chalcocite powder, and uniformly stirring to form a biochar/diatomite/tourmaline powder/chalcocite powder solution;
step 202, placing biochar/diatomite/tourmaline powder/chalcocite powder solution into a planetary high-energy ball mill, wherein the ball milling speed is 200rpm, the ball milling time is 2h, and completing a ball milling process to obtain a cleaning modifier solution;
and 203, taking out the ball-milled cleaning modifier solution, placing the ball-milled cleaning modifier solution in a 180 ℃ oven for drying to constant weight, taking out the dried solid product, and grinding, sieving and dispersing the solid product to obtain the cleaning modifier.
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