A tasteless asphalt additive, tasteless asphalt and a preparation method thereof

Abstract

The application discloses a kind of odorless asphalt additives, odorless asphalt and preparation method thereof.The odorless asphalt additives of the application includes the following components by weight parts: auxiliary odorless agent, 1-5 parts;Modified slow-release odorless microcapsule, 1-5 parts;Dispersing agent, 1-10 parts;The modified slow-release odorless microcapsule includes shell material and core material, wherein the shell material is a composite shell material including silicon dioxide / nano tourmaline / polydopamine, the core material includes one or more of ketones, esters, aldehydes, ethers, and the shell material surface is loaded with metal chelate.The application adds odorless asphalt additives containing modified slow-release odorless microcapsule to asphalt, and with the slow-release effect of microcapsule, it achieves the purpose of efficiently and durably reducing the content of irritating gas in asphalt fumes and emitting pleasant fragrance, while also having good road performance, providing a new approach for the environmental utilization of asphalt.

Description

Technical Field

[0001] This invention belongs to the field of environmentally friendly asphalt, specifically relating to a odor-neutralizing asphalt additive, odor-neutralizing asphalt, and its preparation method. Background Technology

[0002] Asphalt pavement is currently the most common type of road construction, primarily utilizing hot-mix and hot-laying processes during its production and construction. However, the high temperatures during storage and transportation of asphalt materials cause it to release large amounts of toxic, harmful, and irritating fumes into the air, polluting the environment, posing challenges to plant and animal survival, and impacting human health. Related research indicates that asphalt fumes mainly consist of low- and medium-molecular-weight hydrocarbons and their derivatives, primarily PAHs, nitrogen-containing compounds, and sulfur-containing compounds. These include potent carcinogens such as benzo[a]pyrene and gases with irritating odors such as NH3, H2S, and thiophene. Therefore, conducting research on asphalt fume emission reduction is essential.

[0003] Currently, the most commonly used technology for controlling asphalt fume pollution is warm-mix asphalt technology. Essentially, warm-mix asphalt technology allows asphalt mixtures to be mixed, laid, and compacted at relatively low temperatures to save energy and reduce fume emissions. Representative technologies include organic viscosity-reducing warm-mix technology, surfactant-based warm-mix technology, and foamed asphalt warm-mix technology. However, due to the addition of water and additives, the high-temperature performance, low-temperature performance, and water damage resistance of asphalt pavements decrease, leading to a reduction in their service life. Furthermore, warm-mix asphalt technology is relatively expensive, making it difficult to popularize. Summary of the Invention

[0004] To address the problems existing in the prior art, this invention provides a low-odor asphalt additive, low-odor asphalt, and its preparation method. The low-odor asphalt additive, prepared by adding modified slow-release low-odor microcapsules to asphalt, achieves the goal of efficiently and persistently reducing the content of irritating gases in asphalt fumes and emitting a pleasant aroma through the slow-release effect of the microcapsules, while also exhibiting good road performance, providing a new approach for the environmentally friendly utilization of asphalt.

[0005] The first aspect of this invention provides a odor-neutralizing asphalt additive, comprising the following components by weight:

[0006] Deodorizing agent, 1-5 parts;

[0007] Modified sustained-release deodorizing microcapsules, 1-5 parts;

[0008] Dispersant, 1-10 parts;

[0009] The modified sustained-release deodorizing microcapsule comprises a shell material and a core material, wherein the shell material is a composite shell material comprising silica / nano tourmaline / polydopamine, and the core material comprises one or more of ketones, esters, aldehydes, and ethers, and the surface of the shell material is loaded with metal chelates.

[0010] Furthermore, the auxiliary deodorizing agent is selected from one or more of maleamide compounds with more than 4 carbon atoms or antioxidants with more than 20 carbon atoms.

[0011] Furthermore, the maleamide compound having more than 4 carbon atoms is selected from one or more of N-phenylmaleimide, succinimide 6-(maleimino)hexanoate, tris(2-maleiminoethyl)amine, and N-(2-hydroxyethyl)maleimide.

[0012] Further, the antioxidant with more than 20 carbon atoms is a hindered phenolic antioxidant and / or an aryl acid antioxidant with a boiling point greater than 300°C. The hindered phenolic antioxidant with more than 20 carbon atoms is selected from one or more of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2,6-di-tert-butyl-p-methylphenol, and 2,6-di-tert-butyl-p-methylphenol. The aryl acid antioxidant with a boiling point greater than 300°C is selected from one or more of 3-(3,5-dimethyl-4-hydroxyphenyl)acrylic acid, 3-(3,5-dimethoxy-4-hydroxyphenyl)acrylic acid, and 3-(3-methoxy-4-hydroxyphenyl)acrylic acid.

[0013] Furthermore, the dispersant is one or more of dodecyl dimethyl betaine and 1-hydroxyethyl-carboxymethyl-alkyl imidazoline.

[0014] Furthermore, the modified sustained-release deodorizing microcapsules have a particle size of 1-5 μm.

[0015] Furthermore, the mass ratio of the shell material to the core material of the modified sustained-release deodorizing microcapsule is 1:(0.5-2).

[0016] Furthermore, the shell material of the modified sustained-release deodorizing microcapsule is a composite shell material comprising silica / nano tourmaline / polydopamine, wherein the mass ratio of silica to nano tourmaline is (1-5):1, and the mass ratio of silica to polydopamine shell material is 1:(0.1-0.5).

[0017] Furthermore, the shell material surface is loaded with a metal chelate, wherein the metal is preferably copper.

[0018] Furthermore, the shell material surface is loaded with metal chelates, and the metal loading accounts for 0.1wt%-15wt% of the total mass of the sustained-release deodorizing microcapsules.

[0019] Furthermore, the ketone is an aliphatic ketone with more than 4 carbon atoms; the aliphatic ketone with more than 4 carbon atoms is selected from one or more of 3-hydroxy-2-butanone, 2,3-butanedione, and 3-penten-2-one.

[0020] Further, the esters are selected from fatty acid esters with more than 5 carbon atoms and lactones with more than 5 carbon atoms; the fatty acid esters with more than 5 carbon atoms are selected from one or more of butyl acetate, isoamyl acetate, leaf ester acetate, leaf ester isobutyrate, ethyl isovalerate, butyl hexanoate, ethyl laurate, and ethyl octanoate; the lactones with more than 5 carbon atoms are selected from one or more of γ-valerolactone, γ-caprolactone, γ-octyllactone, and γ-nonalactone.

[0021] Further, the aldehydes are selected from aromatic aldehydes with more than 6 carbon atoms and terpenoid aldehydes with more than 8 carbon atoms; the aromatic aldehydes with more than 6 carbon atoms are selected from one or more of benzaldehyde, phenylacetaldehyde, o-methoxy-p-methylbenzaldehyde, and 2-methyl-3-(3,4-methylenedioxyphenyl)propanal; the terpenoid aldehydes with more than 8 carbon atoms are selected from one or more of citral, citronellol, and hydroxycitronellol.

[0022] Furthermore, the ether is an aromatic ether with more than 9 carbon atoms; the aromatic ether with more than 9 carbon atoms is selected from one or more of 4-hydroxy-3-methylallylbenzene and 4-propenyl anisole.

[0023] Furthermore, the preparation method of the modified sustained-release deodorizing microcapsules includes the following steps:

[0024] S1: Mix nano-tourmaline powder, surfactant and solvent, modify under stirring, wash after modification, freeze dry to obtain modified nano-tourmaline powder;

[0025] S2: Mix one or more of ketones, esters, aldehydes, and ethers to obtain a core material mixture;

[0026] S3: Add solvent and modified nano-tourmaline powder obtained in step S1 to the core material mixture obtained in step S2, and stir to mix;

[0027] S4: Add the shell material precursor to the reaction system of step S3, stir and mix to obtain Pickering emulsion;

[0028] S5: Adjust the pH of the Pickering emulsion obtained in step S4 to 2-5, continue stirring, then age, filter, and freeze-dry;

[0029] S6: Add the solid powder obtained in step S5 to the buffer solution, add dopamine hydrochloride, stir and process, then filter, wash and freeze dry;

[0030] S7: Add the solid powder obtained in step S6 to the metal ion salt-formamide solution, stir and process. After the reaction is complete, filter, wash and freeze dry to obtain the modified sustained-release deodorizing microcapsules.

[0031] Furthermore, in step S1, the diameter of the nano-tourmaline powder is 10-100 nm.

[0032] Further, the surfactant mentioned in step S1 is a cationic surfactant, preferably one or more of dodecyl dimethyl benzyl ammonium chloride, hexadecyl trimethyl ammonium bromide, and octadecyl trimethyl ammonium chloride.

[0033] Further, in step S1, the solvent is an aprotic solvent with a boiling point >100℃, preferably one or more of formamide, N,N-dimethylformamide, dimethylacetamide, and dimethylphosphoramide, and more preferably formamide.

[0034] Further, in step S1, the mass ratio of nano-tourmaline powder to surfactant is (1-10):1, and the mass ratio of solvent to surfactant is (10-50):1.

[0035] Further, in step S1, the stirring speed is 400-600 rpm; the modification temperature is 100-200℃; and the modification time is 4-10 hours.

[0036] Furthermore, in step S1, the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

[0037] Furthermore, in step S2, the stirring speed is 400-600 rpm, the stirring temperature is 30-70°C, and the stirring time is 3-10 minutes.

[0038] Further, in step S3, the solvent is an aprotic solvent with a boiling point >100℃, preferably one or more of formamide, N,N-dimethylformamide, dimethylacetamide, and dimethylphosphoramide, and more preferably formamide.

[0039] Further, in step S3, the mass ratio of the core material mixture to the modified nano-tourmaline powder is (1-10):1. The mass ratio of the solvent to the modified nano-tourmaline powder is (20-60):1.

[0040] Furthermore, in step S3, the stirring speed is 400-600 rpm, the stirring temperature is 40-60℃, and the stirring time is 4-6 hours.

[0041] Further, in step S4, the shell material precursor is a silicate ester compound, preferably one or more of methyl silicate, tetraethyl orthosilicate, tetraethyl orthosilicate, and tetrabutyl orthosilicate, and more preferably tetraethyl orthosilicate.

[0042] Further, in step S4, the mass ratio of the core material mixture to the shell material precursor is (0.5-2):1.

[0043] Furthermore, in step S4, the stirring speed is 400-600 rpm, the stirring temperature is 40-60℃, and the stirring time is 4-6 hours.

[0044] Furthermore, in step S5, the pH can be adjusted using a dilute acid, such as dilute hydrochloric acid. The stirring speed is 400-600 rpm, the stirring temperature is 40-60℃, and the stirring time is 4-6 hours.

[0045] Further, in step S5, the aging conditions are: standing at 40-60℃ for 12-30 hours. The freeze-drying conditions are: vacuum drying at -40--20℃ for 4-8 hours.

[0046] Further, in step S6, the buffer solution is one or more of phosphate buffer, carbonate buffer, and tris(hydroxymethyl)aminomethane hydrochloride buffer (Tris buffer), preferably tris(hydroxymethyl)aminomethane hydrochloride buffer (Tris buffer).

[0047] Further, in step S6, the pH value of the buffer solution is 8-10.

[0048] Further, in step S6, the mass ratio of the buffer solution to the solid powder obtained in step S5 is (30-100):1.

[0049] Furthermore, in step S6, after adding dopamine hydrochloride, the mass concentration of dopamine in the reaction system is 2-8 mg / mL.

[0050] Furthermore, in step S6, the stirring speed is 100-300 rpm, the stirring temperature is 20-30℃, and the stirring time is 12-24 h.

[0051] Furthermore, in step S6, the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

[0052] Furthermore, in step S7, the solid powder obtained after freeze-drying in step S6 is dispersed in a metal ion salt-formamide solution, which can be done by ultrasonic dispersion.

[0053] Further, in step S7, the metal ion salt is preferably a copper ion salt, and more preferably anhydrous copper sulfate.

[0054] Further, in step S7, the mass ratio of the metal ion salt to formamide in the metal ion salt-formamide solution is (0.5-1.5):1.

[0055] Further, in step S7, the mass ratio of the metal ion salt-formamide solution to the solid powder obtained in step S7 is (5-20):1.

[0056] Furthermore, in step S7, the stirring speed is 200-450 rpm, the stirring temperature is 100-180℃, and the stirring time is 2-5 hours.

[0057] Furthermore, in step S7, the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

[0058] Further, the auxiliary deodorizing agent is added to the dispersant and stirred at 400-500 rpm for 1-3 hours at 25-45℃. Then, the modified slow-release deodorizing microcapsules are added and stirring is continued for 1-2 hours to obtain the deodorizing asphalt additive.

[0059] A second aspect of the present invention provides an odor-neutralizing asphalt, comprising the following components by weight:

[0060] Base bitumen, 50-500 parts;

[0061] The above-mentioned odor-neutralizing asphalt additive, 1-50 parts.

[0062] Furthermore, the base asphalt is commercially available No. 50, No. 70 and No. 90 road asphalt, preferably No. 70 Grade A asphalt.

[0063] Further, heat the base asphalt to 133-153℃, add the odor-neutralizing asphalt additive at a speed of 400-600 rpm, and stir for 2-4 hours to obtain the odor-neutralizing asphalt.

[0064] Compared with the prior art, the present invention has the following advantages:

[0065] (1) The modified slow-release odor-neutralizing microcapsules contained in the odor-neutralizing asphalt additive of the present invention have a triple effect in their composite shell material. The first effect is that during the preparation process, nano-tourmaline serves as a template agent for the synthesis of microcapsules, which can maintain the stability of the core material precursor. The second effect is that during the copper ion modification process of the microcapsule composite shell material, the negative ion field released by nano-tourmaline powder under high temperature conditions is used to adsorb a large number of copper ions onto the surface of the microcapsules, effectively increasing the metal ion loading of the microcapsule shell material and further enhancing the smoke suppression ability of the modified slow-release odor-neutralizing microcapsules. The third effect is that during the asphalt mixing process, under the action of high temperature, the nano-tourmaline powder contained inside the modified slow-release odor-neutralizing microcapsule shell material will release a negative ion field, further attracting the compounds released by the asphalt under the action of high temperature to the vicinity of the modified slow-release odor-neutralizing microcapsules. While increasing the difficulty of volatilization of these compounds, it can make the metal ions on the surface of the microcapsules and the odor-neutralizing core material components released by the microcapsules react with more of the above-mentioned compounds, thereby effectively reducing the impact of irritating gases released by asphalt pavement on the human body.

[0066] (2) In the odor-neutralizing asphalt of the present invention, the modified slow-release odor-neutralizing microcapsules can slowly release the core material - odor-neutralizing active components after the asphalt is added. When the odor-neutralizing active components are released onto the surface of the microcapsule shell, they can undergo a nucleophilic reaction with compounds in the asphalt that have irritating odors to generate compounds with higher stability and boiling points. These compounds are difficult to decompose and volatilize during high-temperature asphalt construction, thereby achieving the purpose of reducing the irritating odor of asphalt fumes. At the same time, microencapsulating the odor-neutralizing active components can also effectively prevent them from reacting in time due to rapid volatilization at high temperatures. While extending the action time of the odor-neutralizing active components, it also further improves their safety of use.

[0067] (3) The modified slow-release odor-neutralizing microcapsules added to the odor-neutralizing asphalt of the present invention are small in size, and their outer layer is a polydopamine film that can interact with the polar molecules in the asphalt and has good compatibility with the asphalt. Therefore, after being added to the asphalt, it can effectively avoid affecting the asphalt road performance.

[0068] (4) In the odor-neutralizing asphalt of the present invention, the surface of the modified slow-release odor-neutralizing microcapsules is modified with a large number of copper ions through chelation. These copper ions can capture some more active sulfur-containing and nitrogen-containing compounds with irritating odors in the asphalt, form π-complexes, avoid their volatilization at high temperature, and further reduce the irritating odor of asphalt fumes.

[0069] (5) The odor-neutralizing asphalt of the present invention can also undergo nucleophilic reaction with compounds in the asphalt that have irritating odors to generate compounds with higher stability and boiling point, thereby reducing the irritating odor of asphalt fumes. Moreover, the auxiliary odor-neutralizing agent has a higher boiling point and exerts its maximum odor-neutralizing effect faster than the modified slow-release odor-neutralizing microcapsules. While ensuring safety and odor-neutralizing effect, it makes up for the defect that the modified slow-release odor-neutralizing microcapsules cannot play a role immediately after being added to asphalt. Attached Figure Description

[0070] Figure 1 This is a scanning electron microscope image of the modified sustained-release deodorizing microcapsules prepared in Example 1. Detailed Implementation

[0071] To further illustrate the technical solution of the present invention, the present invention will be clearly and thoroughly described below in conjunction with embodiments.

[0072] The morphology of the slow-release modified microcapsules described in this invention was tested by scanning electron microscopy with an accelerating voltage of 20kV. Since the microcapsule wall material is non-conductive, the sample needs to be sputtered with gold before testing.

[0073] The sustained-release modified microcapsules of the present invention were subjected to surface elemental analysis using X-ray energy dispersive spectroscopy to confirm that copper ions were successfully modified onto the surface of the microcapsules.

[0074] The sulfides in the odor-free asphalt flue gas described in this invention are tested by gas chromatography according to the national standard GB / T 14678-1993, "Determination of hydrogen sulfide, methanethiol, dimethyl sulfide and dimethyl disulfide in air quality".

[0075] The base asphalt used in the following examples and comparative examples is Sinopec Donghai brand No. 70 Grade A asphalt.

[0076] Example 1

[0077] S1: Add 40nm diameter tourmaline powder, dodecyl dimethyl benzyl ammonium chloride, and formamide to the first container in a mass ratio of 2:1:30. Stir at 180℃ and 400 rpm for 5 hours, then wash with ethanol multiple times and vacuum dry at -30℃ for 5 hours to obtain modified tourmaline powder for later use.

[0078] S2: Add 3-hydroxy-2-butanone, leaf ester acetate, γ-octyl lactone, o-methoxy-p-methylbenzaldehyde, citral, and 4-hydroxy-3-methylallylbenzene in the second container and mix them in the same mass ratio. Stir at 400 rpm for 10 min at 50°C to obtain the core material mixture.

[0079] S3: Add the modified nano-tourmaline powder and formamide obtained in step S1 to the reaction system of step S2. The mass ratio of the core material mixture, modified nano-tourmaline powder and formamide is 2:1:20. Continue stirring at 400 rpm for 5 hours at 50°C.

[0080] S4: Add tetraethyl orthosilicate to the reaction system of step S3. The mass ratio of the core material mixture to tetraethyl orthosilicate is 1:1. Continue stirring at 400 rpm for 5 hours at 50°C to obtain Pickering emulsion.

[0081] S5: Slowly add 10wt% dilute hydrochloric acid to the reaction system in step S4 using a peristaltic pump until the pH of the reaction system is 4. Continue stirring at 400 rpm for 5 hours at 50°C, then stop stirring and age at the same temperature for 24 hours. After that, filter and wash the solid powder in the reaction system and vacuum dry it at -30°C for 5 hours.

[0082] S6: Add the solid powder obtained in step S5 to Tris buffer solution with a pH of 8.5. The mass ratio of Tris buffer solution to solid powder is 50:1. Then add dopamine hydrochloride to make the concentration of dopamine in the reaction system 2 mg / mL. Stir the reaction at 200 rpm at 25°C for 12 h. Finally, filter and wash the bottom solid powder and vacuum dry it at -30°C for 5 h.

[0083] S7: The solid powder obtained in step S6 was ultrasonically dispersed in a 50 wt% anhydrous copper sulfate-formamide solution, with a mass ratio of solid powder to anhydrous copper sulfate-formamide solution of 1:10. The mixture was stirred at 400 rpm and 140°C for 2 hours. After the reaction was completed, the bottom solid powder was filtered and washed, and then vacuum dried at -30°C for 5 hours to obtain the modified sustained-release deodorizing microcapsules. The electron micrograph is shown below. Figure 1 .

[0084] The auxiliary deodorizing agent N-phenylmaleimide, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and 3-(3,5-dimethyl-4-hydroxyphenyl)acrylic acid were mixed in equal mass ratio and dispersed in 1-hydroxyethyl-carboxymethyl-alkylimidazoline. The mixture was stirred at 400 rpm for 1 hour at 25°C. Then, the modified slow-release deodorizing microcapsules prepared in step S7 were added, and the mixture was stirred for another hour to obtain the deodorizing asphalt additive. The mass ratio of the auxiliary deodorizing agent, the modified slow-release deodorizing microcapsules, and 1-hydroxyethyl-carboxymethyl-alkylimidazoline was 1:1:2.

[0085] Heat the base asphalt to 143°C, add the above-mentioned odor-neutralizing asphalt additive at 500 rpm, and stir for 2 hours to obtain odor-neutralizing asphalt. The mass ratio of odor-neutralizing asphalt additive to base asphalt is 4:50.

[0086] Example 2

[0087] Except for step S2, in which the core material mixture is made by mixing 2,3-butanedione, ethyl isovalerate, γ-valerolactone, phenylacetaldehyde, citronellol, and 4-propenyl anisole in the same mass ratio, the rest is the same as in Example 1.

[0088] Example 3

[0089] Except that the mass ratio of auxiliary deodorizing agent, modified slow-release deodorizing microcapsule, and 1-hydroxyethyl-carboxymethyl-alkylimidazoline is 2:1:5 when preparing the deodorizing asphalt additive, the rest is the same as in Example 1.

[0090] Example 4

[0091] Except that when preparing the odor-neutralizing asphalt additive, the auxiliary odor-neutralizing agent is a mixture of succinimide 6-(maleimide)hexanoate, 2,6-di-tert-butyl-p-methylphenol, and 3-(3,5-dimethoxy-4-hydroxyphenyl)acrylic acid in equal mass ratios, the rest is the same as in Example 1.

[0092] Example 5

[0093] Except for the use of dodecyl dimethyl betaine as the dispersant in the preparation of the odor-neutralizing asphalt additive, the other steps are the same as in Example 1.

[0094] Example 6

[0095] Except for step S3, where the mass ratio of the core material mixture, modified nano-tourmaline powder, and formamide is 5:1:20, the other steps are the same as in Example 1.

[0096] Example 7

[0097] Except for step S7, where the mass ratio of solid powder to anhydrous copper sulfate-formamide solution is 1:5, the other steps are the same as in Example 1.

[0098] Comparative Example 1

[0099] S1: Add 3-hydroxy-2-butanone, leaf ester acetate, γ-octyl lactone, o-methoxy-p-methylbenzaldehyde, citral, and 4-hydroxy-3-methylallylbenzene in the same mass ratio to a container, and stir at 400 rpm for 10 min at 50°C to obtain the core material mixture.

[0100] The auxiliary deodorizing agent active components N-phenylmaleimide, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and 3-(3,5-dimethyl-4-hydroxyphenyl)acrylic acid were mixed in equal mass ratio and dispersed in 1-hydroxyethyl-carboxymethyl-alkylimidazoline. The mixture was stirred at 400 rpm for 1 hour at 25°C. Then, the core material mixture obtained in step S1 was added, and stirring was continued for another hour to obtain the deodorizing asphalt additive. The mass ratio of the auxiliary deodorizing agent, the core material mixture, and 1-hydroxyethyl-carboxymethyl-alkylimidazoline was 1:1:2.

[0101] Heat the base asphalt to 143℃, add the odor-neutralizing asphalt additive at 500 rpm, and stir for 2 hours to obtain the odor-neutralizing asphalt. The mass ratio of the odor-neutralizing asphalt additive to the base asphalt is 4:50.

[0102] Comparative Example 2

[0103] The preparation of the modified sustained-release deodorizing microcapsules is the same as in Example 1.

[0104] The odor-neutralizing asphalt additive is prepared by mixing the auxiliary odor neutralizer active components N-phenylmaleimide, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and 3-(3,5-dimethyl-4-hydroxyphenyl)acrylic acid in an equal mass ratio, and then adding the modified slow-release odor-neutralizing microcapsules prepared by S8. The mass ratio of the auxiliary odor neutralizer to the modified slow-release odor-neutralizing microcapsules is 1:1.

[0105] Heat the base asphalt to 143℃, add the odor-neutralizing asphalt additive at 500 rpm, and stir for 2 hours to obtain the odor-neutralizing asphalt. The mass ratio of the odor-neutralizing asphalt additive to the base asphalt is 4:50.

[0106] Comparative Example 3

[0107] Steps S1-S6 are the same as in Example 1;

[0108] The auxiliary deodorizing agent active components N-phenylmaleimide, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and 3-(3,5-dimethyl-4-hydroxyphenyl)acrylic acid were mixed in equal mass ratio and dispersed in 1-hydroxyethyl-carboxymethyl-alkylimidazoline. The mixture was stirred at 400 rpm for 1 hour at 25°C. Then, the solid powder obtained by S6 was added, and the mixture was stirred for another hour to obtain the deodorizing asphalt additive. The mass ratio of the auxiliary deodorizing agent, solid powder, and 1-hydroxyethyl-carboxymethyl-alkylimidazoline was 1:1:2.

[0109] Heat the base asphalt to 143℃, add the odor-neutralizing asphalt additive at 500 rpm, and stir for 2 hours to obtain the odor-neutralizing asphalt. The mass ratio of the odor-neutralizing asphalt additive to the base asphalt is 4:50.

[0110] Comparative Example 4

[0111] S1: Add 3-hydroxy-2-butanone, leaf ester acetate, γ-octyl lactone, o-methoxy-p-methylbenzaldehyde, citral, and 4-hydroxy-3-methylallylbenzene in the same mass ratio to a container, and stir at 400 rpm for 10 min at 50°C to obtain the core material mixture.

[0112] S2: Add dodecyl dimethyl benzyl ammonium chloride and formamide to the reaction system of step S1. The mass ratio of the core material mixture, dodecyl dimethyl benzyl ammonium chloride and formamide is 2:1:20. Continue stirring at 400 rpm for 5 hours at 50°C.

[0113] S3: Add tetraethyl orthosilicate to the reaction system of step S2. The mass ratio of core material mixture to tetraethyl orthosilicate is 1:1. Continue stirring at 400 rpm for 5 hours at 50°C to obtain an emulsion.

[0114] S4: Slowly add 10wt% dilute hydrochloric acid to the reaction system in step S3 using a peristaltic pump until the pH of the reaction system is 4. Continue stirring at 400 rpm for 5 hours at 50°C, then stop stirring and age at the same temperature for 24 hours. After that, filter and wash the solid powder in the reaction system and vacuum dry it at -30°C for 5 hours.

[0115] S5: Add the solid powder obtained in step S4 to Tris buffer solution with a pH of 8.5. The mass ratio of Tris buffer solution to solid powder is 50:1. Then add dopamine hydrochloride to make the concentration of dopamine in the reaction system 2 mg / mL. Stir the reaction at 200 rpm at 25°C for 12 h. Finally, filter and wash the bottom solid powder and vacuum dry it at -30°C for 5 h.

[0116] S6: The solid powder obtained in step S5 is ultrasonically dispersed in a 50wt% anhydrous copper sulfate-formamide solution. The mass ratio of the solid powder to the anhydrous copper sulfate-formamide solution is 1:10. The mixture is stirred and reacted at 400 rpm and 140°C for 2 hours. After the reaction is completed, the bottom solid powder is filtered and washed, and then vacuum dried at -30°C for 5 hours to obtain the modified sustained-release deodorizing microcapsules.

[0117] The auxiliary deodorizing agent N-phenylmaleimide, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and 3-(3,5-dimethyl-4-hydroxyphenyl)acrylic acid were mixed in equal mass ratio and dispersed in 1-hydroxyethyl-carboxymethyl-alkylimidazoline. The mixture was stirred at 400 rpm for 1 hour at 25°C. Then, the modified slow-release deodorizing microcapsules prepared in step S6 were added, and the mixture was stirred for another 1 hour to obtain the deodorizing asphalt additive. The mass ratio of the auxiliary deodorizing agent, the modified slow-release deodorizing microcapsules, and the 1-hydroxyethyl-carboxymethyl-alkylimidazoline was 1:1:2.

[0118] Heat the base asphalt to 143℃, add the odor-neutralizing asphalt additive at 500 rpm, and stir for 2 hours to obtain the odor-neutralizing asphalt. The mass ratio of the odor-neutralizing asphalt additive to the base asphalt is 4:50.

[0119] Test case

[0120] Sulfides are the main cause of the pungent odor of asphalt fumes. Odorless asphalt was prepared using Sinopec Donghai brand No. 70 Grade A asphalt. The asphalt prepared in the examples and comparative examples was stored at 143°C for 0 days, 7 days, and 30 days. Then, equal masses of the stored asphalt were transferred to a sealed container, and fumes were enriched at 163°C and 300 rpm for 4 hours. After enrichment, the gas in the sealed container was extracted, and the sulfide content in the gas was tested using gas chromatography. The data are shown in Table 1 below.

[0121] Table 1 Gas chromatography sulfide test data

[0122]

[0123] It should be emphasized that the above-mentioned content is only a specific embodiment of the present invention and should not be construed as limiting the present invention to the above description in specific implementation. For researchers and those skilled in the art to which this invention pertains, any simple deductions and improvements made without departing from the spirit and principles of the present invention should be considered within the scope of protection of the present invention.

Claims

1. A deodorized asphalt additive characterized by: By weight parts include the following components: Auxiliary odor removal agent, 1-5 parts; Modified slow-release odor removal microcapsule, 1-5 parts; Dispersing agent, 1-10 parts; The modified slow-release odor removal microcapsule comprises a shell material and a core material, wherein the shell material is a composite shell material comprising silicon dioxide / nano tourmaline / polydopamine, and the core material comprises one or more of ketones, esters, aldehydes and ethers, and the shell material surface is loaded with metal chelates; The auxiliary odor removal agent is selected from one or more of maleic amide compounds with more than 4 carbon atoms or antioxidants with more than 20 carbon atoms; The shell material surface of the modified slow-release odor removal microcapsule is loaded with metal chelates, wherein the metal is copper; The ketones are aliphatic ketones with more than 4 carbon atoms, the esters are selected from fatty acid esters with more than 5 carbon atoms and lactones with more than 5 carbon atoms, the aldehydes are selected from aromatic aldehydes with more than 6 carbon atoms and terpene aldehydes with more than 8 carbon atoms, and the ethers are aromatic ethers with more than 9 carbon atoms; The modified slow-release odor removal microcapsule is prepared by the following method, comprising: S1: Mix nano tourmaline powder, surfactant and solvent, modify under stirring, wash after modification, freeze-dry to obtain modified nano tourmaline powder; S2: Stir and mix one or more of ketones, esters, aldehydes and ethers to obtain a core material mixture; S3: Add solvent and modified nano tourmaline powder obtained in step S1 to the core material mixture obtained in step S2 and stir and mix; S4: Add shell material precursor to the reaction system in step S3, stir and mix to obtain a Pickering emulsion; S5: Adjust the pH value of the Pickering emulsion obtained in step S4 to 2-5, continue stirring, then age, filter and freeze-dry; S6: Add the solid powder prepared in step S5 to a buffer solution, add dopamine hydrochloride, stir and treat, then filter, wash and freeze-dry; S7: Add the solid powder prepared in step S6 to a copper ion salt-formamide solution, stir and treat, after the reaction is completed, filter, wash and freeze-dry to obtain the modified slow-release odor removal microcapsule.

2. The taste-free asphalt additive according to claim 1, characterized in that: The maleic amide compounds with more than 4 carbon atoms are selected from one or more of N-phenylmaleimide, 6-(maleimido) hexanoic acid succinimidyl ester, tris(2-maleimidoethyl)amine and N-(2-hydroxyethyl)maleimide; And / or, the antioxidant with more than 20 carbon atoms is a hindered phenolic antioxidant and / or an aryl acid antioxidant with a boiling point greater than 300℃; the hindered phenolic antioxidant with more than 20 carbon atoms is selected from one or more of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2,6-di-tert-butyl-p-methylphenol and 2,6-di-tert-butyl-p-methylphenol; the aryl acid antioxidant with a boiling point greater than 300℃ is selected from one or more of 3-(3,5-dimethyl-4-hydroxyphenyl)acrylic acid, 3-(3,5-dimethoxy-4-hydroxyphenyl)acrylic acid and 3-(3-methoxy-4-hydroxyphenyl)acrylic acid.

3. The taste-free asphalt additive according to claim 1, characterized in that: The dispersant is one or more of dodecyl dimethyl betaine, 1-hydroxyethyl-carboxymethyl-alkyl imidazoline.

4. The taste-free asphalt additive according to claim 1, characterized in that: The modified slow-release deodorant microcapsule has a particle size of 1-5 microns.

5. The taste-free asphalt additive according to claim 1, characterized in that: The modified slow-release deodorant microcapsule has a mass ratio of shell material to core material of 1:(0.5-2).

6. The taste-free asphalt additive according to claim 1, characterized in that: The shell material of the modified slow-release deodorant microcapsule is a composite shell material comprising silicon dioxide / nano tourmaline / polydopamine, wherein the mass ratio of silicon dioxide to nano tourmaline is (1-5):1, and the mass ratio of silicon dioxide to polydopamine shell material is 1:(0.1-0.5).

7. The taste-free asphalt additive according to claim 1, characterized in that: The metal loading on the surface of the shell material of the modified slow-release deodorant microcapsule accounts for 0.1wt%-15wt% of the total mass of the modified slow-release deodorant microcapsule.

8. The taste-free asphalt additive according to claim 1, characterized in that: The aliphatic ketone with more than 4 carbon atoms is selected from one or more of 3-hydroxy-2-butanone, 2,3-butanedione, and 3-penten-2-one; And / or, the fatty acid ester with more than 5 carbon atoms is selected from one or more of butyl acetate, isoamyl acetate, linalyl acetate, linalyl iso-butyrate, ethyl iso-valerate, butyl hexanoate, ethyl laurate, and ethyl octanoate; the lactone with more than 5 carbon atoms is selected from one or more of gamma-valerolactone, gamma-hexalactone, gamma-octalactone, and gamma-nonalactone; And / or, the aromatic aldehyde with more than 6 carbon atoms is selected from one or more of benzaldehyde, phenylacetaldehyde, o-methoxy-p-methylbenzaldehyde, and 2-methyl-3-(3,4-methylene-dioxyphenyl)propanal; the terpene aldehyde with more than 8 carbon atoms is selected from one or more of citral, citronellal, and hydroxy-citronellal; And / or, the aromatic ether with more than 9 carbon atoms is selected from one or more of 4-hydroxy-3-methylallylbenzene and 4-propenyl anisole.

9. The taste-free asphalt additive according to claim 1, characterized in that: The surface active agent in step S1 is a cationic surface active agent, and the solvent is an aprotic solvent with a boiling point >100℃; And / or, the mass ratio of nano tourmaline powder to surface active agent is (1-10):1, and the mass ratio of solvent to surface active agent is (10-50):

1.

10. The taste-free asphalt additive according to claim 9, characterized in that: The surface active agent in step S1 is one or more of dodecyl dimethyl benzyl ammonium chloride, hexadecyl trimethyl ammonium bromide, and octadecyl trimethyl ammonium chloride; and the solvent is one or more of formamide, N,N-dimethylformamide, dimethylacetamide, and dimethylphosphoryl amide.

11. The taste-free asphalt additive according to claim 1, characterized in that: In step S1, the stirring speed is 400-600 revolutions per minute; the modification temperature is 100-200℃, and the modification time is 4-10 hours; And / or, in step S2, the stirring speed is 400-600 revolutions per minute, the stirring temperature is 30-70℃, and the stirring time is 3-10 minutes; And / or, in step S3, the stirring speed is 400-600 revolutions per minute, the stirring temperature is 40-60℃, and the stirring time is 4-6 hours; And / or, in step S4, the stirring speed is 400-600 revolutions per minute, the stirring temperature is 40-60℃, and the stirring time is 4-6 hours; And / or, in step S5, the stirring speed is 400-600 rpm, the stirring temperature is 40-60℃, and the stirring time is 4-6 hours. And / or, in step S6, the stirring speed is 100-300 rpm, the stirring temperature is 20-30℃, and the stirring time is 12-24 hours. And / or, in step S7, the stirring speed is 200-450 rpm, the stirring temperature is 100-180℃, and the stirring time is 2-5 hours.

12. The taste-free asphalt additive according to claim 1, characterized in that: In step S3, the solvent is an aprotic solvent with a boiling point >100℃.

13. The taste-free asphalt additive according to claim 12, characterized in that: In step S3, the solvent is one or more of formamide, N,N-dimethylformamide, dimethylacetamide, and dimethylphosphoramidate.

14. The taste-free asphalt additive according to claim 1, characterized in that: In step S4, the shell precursor is a silicate compound. And / or, the mass ratio of the core material mixture to the shell precursor is (0.5-2):

1.

15. The taste-free asphalt additive according to claim 14, characterized in that: In step S4, the shell precursor is one or more of methyl silicate, ethyl silicate, tetraethyl silicate, and butyl silicate.

16. The taste-free asphalt additive according to claim 1, characterized in that: In step S6, the buffer is one or more of phosphate buffer, carbonate buffer, and tris-hydroxymethyl aminomethane hydrochloride buffer, and the pH value of the buffer is 8-10. And / or, the mass ratio of the buffer to the solid powder prepared in step S5 is (30-100):

1.

17. The taste-free asphalt additive according to claim 1, characterized in that: In step S6, after adding dopamine hydrochloride, the mass concentration of dopamine in the reaction system is 2-8 mg / mL.

18. The taste-free asphalt additive according to claim 1, characterized in that: In step S7, the metal copper ion salt is anhydrous copper sulfate. And / or, in the metal copper ion salt-formamide solution, the mass ratio of the metal copper ion salt to formamide is (0.5-1.5):

1. And / or, the mass ratio of the metal copper ion salt-formamide solution to the solid powder prepared in step S7 is (5-20):

1.

19. A deodorized bitumen characterized by: The following components are included by weight parts: Matrix asphalt, 50-500 parts; The odorless asphalt additive of any one of claims 1-18, 1-50 parts.

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