Functionalized hollow mesoporous silica support oil regeneration particles, and methods of making and using the same

Abstract

The present application relates to the field of road material regeneration technology and maintenance, in particular to a kind of functional hollow mesoporous silica oil-loaded regeneration particle and its preparation method and application.The present application is aimed at the seriously aged asphalt pavement of more than 5 years in service, ≤40 mm in penetration and ≥55 DEG C in softening point, adopts high oil-loading rate alkyl-pyridine gradient functional hollow mesoporous silica nano-regeneration particle, and is added to milling material with the super-low dosage of 2%~6% of RAP mass;Under the low-temperature mixing of 120~140 DEG C, the regeneration agent is released and penetrates through mesoporous channel, and then is laid at high speed of 4~5 m / min through in-situ hot recycling unit, and is compacted at >110 DEG C, to realize the regeneration of aged asphalt.The present application solves the problems of high energy consumption and serious volatilization loss of regeneration agent caused by high temperature and high dosage in traditional process, and improves construction efficiency and regeneration effect.

Description

Technical Field

[0001] This invention relates to the field of road material recycling technology and maintenance, specifically to a functionalized hollow mesoporous silica oil-loaded regenerated particle, its preparation method, and its application. Background Technology

[0002] Asphalt pavements are exposed to a complex environment for extended periods, and are highly susceptible to aging due to the combined effects of sunlight, temperature, oxygen, and rainwater. This leads to cracking, loosening, and other defects, reducing pavement durability. Asphalt aging is primarily caused by the following factors: ① Thermal-oxidative aging: During production, transportation, mixing, and use, high temperatures (such as 170℃ during the mixing stage) accelerate oxidation reactions, triggering free radical chain reactions. This results in the volatilization of light components and the conversion of aromatics into resins and asphaltenes, causing the asphalt to harden and become brittle. ② Photo-oxidative aging: Ultraviolet radiation (wavelength 290~400 nm) damages the C-C and CH bonds in asphalt molecules, forming free radicals and initiating condensation reactions, further exacerbating the deterioration of the colloidal structure. ③ Water aging: Moisture penetration causes the loss of soluble substances from within the asphalt, and changes in interfacial tension accelerate oxidation, reducing adhesion to aggregates.

[0003] For aging asphalt, the industry generally adopts recycling technology. Recycling agents are mainly divided into two categories according to the source of raw materials: ① Petroleum-based recycling agents: mainly based on petroleum fractions (such as aromatic oils and light diesel oil), often with the addition of tackifying resins (such as butadiene-acrylate copolymers) to improve stability; ② Bio-based recycling agents: utilizing biomass raw materials such as vegetable oils and waste oils, combining environmental protection and sustainability. The main components of asphalt pavement are asphalt, aggregates, mineral powder, and additives. Among them, asphalt, as the main binder, plays a key role in the service level and durability of asphalt pavement. Asphalt has a complex chemical composition, containing a variety of hydrocarbons, and is extremely prone to aging under environmental influences, while mineral aggregates basically do not age.

[0004] Asphalt aging accompanies asphalt pavements throughout their entire lifecycle, profoundly impacting their performance and service life. Improving the anti-aging properties of asphalt is key to extending the service life of asphalt pavements and reducing maintenance costs. Therefore, it is necessary to develop high-oil-load nano-recycling particles suitable for in-situ thermal recycling of asphalt pavements to deeply improve aging, extend the service life of asphalt pavements, and reduce maintenance costs. Summary of the Invention

[0005] To achieve one of the above objectives, this invention proposes a functionalized hollow mesoporous silica-loaded oil-regenerating particle, its preparation method, and its application. Targeting the aging phenomenon of asphalt pavements, this invention uses hollow mesoporous silica as a carrier to load a regenerating agent, achieving in-situ thermal regeneration of asphalt pavements. The large internal cavity and mesoporous structure of hollow mesoporous silica can effectively load the regenerating agent, reducing its volatilization during the asphalt aging regeneration process. Furthermore, using hollow mesoporous silica as a carrier for loading the regenerating agent results in better dispersibility in asphalt, allowing for deeper improvement of aging processes, extending the service life of asphalt pavements, and reducing maintenance costs. The technical solution of this invention is implemented as follows:

[0006] In a first aspect, the present invention provides a functionalized hollow mesoporous silica oil-loaded regenerating particle, which is prepared by functionalized hollow mesoporous silica loaded with a regenerating agent; the functionalized hollow mesoporous silica is modified by a gradient of alkyl and pyridine groups; the regenerating agent includes at least one of petroleum distillate oil, bio-oil and recycled waste oil.

[0007] Preferably, the petroleum distillate includes furfural extract oil and aromatic oil, the bio-oil includes waste edible oil, and the recycled waste oil includes waste engine oil.

[0008] Preferably, the synthesis method of the functionalized hollow mesoporous silica includes the sacrificial template method, self-templating method, soft template method, hard template method, and sol-gel method, wherein the template size needs to be controlled at 200~900 nm and the silicon source hydrolysis rate at 0.01~0.5 h. -1 When the calcination temperature is 500~800 ℃, a structure with hollow cavities and mesoporous channels can be formed.

[0009] Preferably, the functionalized hollow mesoporous silica has a particle size of 300~1110 nm, a mesopore diameter of 2~5 nm, a shell thickness of 20~100 nm, and a specific surface area of ​​600~1200 m². 2 / g, hollow cavities account for 82%~87% of the particle diameter.

[0010] Secondly, the present invention provides a method for preparing functionalized hollow mesoporous silica, used for the above-mentioned functionalized hollow mesoporous silica oil-loaded regenerated particles, comprising the following steps:

[0011] S1. Mix deionized water and ethanol, adjust the pH, add 3-aminophenol and formaldehyde solution while stirring to obtain a mixture and form phenolic resin microspheres.

[0012] S2. Add surfactant, triethanolamine and silicon source to the above mixture and stir;

[0013] S3. Centrifuge, wash, and dry the above mixture, and remove the surfactant to obtain hollow mesoporous silica particles.

[0014] S4. The above hollow mesoporous silica particles are placed in an ethanol aqueous solution and stirred. The pH is adjusted, and then a silane coupling agent is added to obtain a suspension. After centrifugation, washing and drying, surface alkyl-modified hollow mesoporous silica is obtained.

[0015] S5. Dissolve 4-pyridinecarboxylic acid in buffer solution, add 1-ethyl-carbodiimide hydrochloride and N-hydroxysuccinimide and stir to obtain an activation solution. Then, put the surface alkyl-modified hollow mesoporous silica from step S4 into the above activation solution and react in the dark to obtain a hollow mesoporous silica support with alkyl and pyridine group gradient modification.

[0016] Preferably, the method for removing surfactant in step S3 includes calcination, solvent extraction, and chemical etching.

[0017] More preferably, in step S4, the mass ratio of silane coupling agent to hollow mesoporous silica particles is (3-4):1; and in step S5, the mass ratio of 4-pyridinecarboxylic acid to surface alkyl-modified hollow mesoporous silica particles is (0.3-0.5):1.

[0018] Preferably, the silicon source in step S2 includes one of tetraethyl orthosilicate (TEOS), methyltrimethoxysilane (MTMS), methyltriethoxysilane (MTES), 3-aminopropyltriethoxysilane (APTES), methyl orthosilicate, propyl orthosilicate, and butyl orthosilicate; the surfactant in step S3 includes one of hexadecyltrimethylammonium chloride (CTAC), hexadecyltrimethylammonium bromide (CTAB), hexadecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, and octadecyltrimethylammonium bromide; and the silane coupling agent in step S4 includes hexamethyldisilazane (HMDS), trimethylchlorosilane (TMCS), and octadecyltrimethoxysilane (ODS, C 18 H 37 One of Si(OCH3)3 and γ-aminopropyltriethoxysilane (KH-550).

[0019] In a further preferred embodiment, the silane-modified hollow mesoporous silica in step S4 changes from a hydrophilic material rich in carbonyl groups to an oleophilic material with organic functional groups, exhibiting good oleophilic and hydrophobic properties. -NH2 forms hydrogen bonds with polar components of asphalt (such as asphaltenes), enhancing the bonding force between the carrier and asphalt interface. The silane layer is stable at 180 °C, delaying the high-temperature decomposition of the regenerator.

[0020] In a further preferred embodiment, step S5 involves modifying hollow mesoporous silica with pyridine to provide it with pyridine polar adsorption groups. This enhances the adsorption capacity of aromatics in the regenerator component through π-π stacking or hydrogen bonding, thereby increasing its oil carrying capacity and achieving targeted sustained release. The pyridine nitrogen atoms capture free radicals generated by ultraviolet aging, interrupting the oxidation chain reaction.

[0021] Thirdly, the present invention provides a method for preparing the functionalized hollow mesoporous silica oil-carrying regenerated particles described in the first aspect, comprising the following steps: adding a regenerating agent and functionalized hollow mesoporous silica into a solvent, mixing and stirring under negative pressure, with an absolute value of vacuum pressure difference of 0.05~0.2 MPa, drying after vacuum adsorption, to obtain the functionalized hollow mesoporous silica oil-carrying regenerated particles.

[0022] Preferably, the mass ratio of the regenerator to the functionalized hollow mesoporous silica is (4-5):1.

[0023] Further preferred, the oil loading can be calculated using formula (1) based on the shell thickness, hollow cavity volume, specific surface area of ​​the hollow mesoporous silica, the pressure difference of vacuum adsorption during the preparation process, and the contact angle between the carrier and the oil. The formula is fitted based on the various parameters of the hollow mesoporous silica and the conditions of the loaded regenerator, including the following:

[0024] (1)

[0025] The parameters in the formula are: L oil Oil load factor, in %; ρ oil The density of the oil it carries is expressed in g / cm³. 3 V hollow The volume of the hollow cavity in the mesoporous silica is expressed in cm³. 3 / g;S meso This refers to the mesoporous specific surface area of ​​hollow mesoporous silica, in m³. 2 / g; This is the absolute value of the vacuum pressure difference, in MPa. This is the oil-carrier contact angle, in degrees (°). The viscosity is expressed as oil, in mPa·s. The particle packing porosity is 0.75.

[0026] Preferably, the oil loading rate of the functionalized hollow mesoporous silica oil-loaded regenerated particles is 320%~370%.

[0027] Fourthly, the present invention provides the application of the functionalized hollow mesoporous silica oil-loaded regeneration particles described in the first aspect, characterized in that the applicable scenarios of the functionalized hollow mesoporous silica oil-loaded regeneration particles include in-situ hot recycling of asphalt pavement, hot recycling of aged asphalt pavement mixed at the plant, cold recycling of aged asphalt pavement mixed at the plant, in-situ cold recycling of asphalt pavement, and full-depth recycling of asphalt pavement.

[0028] Fifthly, the present invention provides a method for applying the functionalized hollow mesoporous silica oil-loaded regenerated particles described in the first aspect, comprising the following steps:

[0029] A1. Milling aged asphalt pavement to obtain recycled asphalt RAP mixture;

[0030] A2. The functionalized hollow mesoporous silica oil-carrying regenerated particles are added to the mixture at an amount of 2-6% of the mass of the above-mentioned recycled asphalt RAP mixture;

[0031] A3. Heat and mix the recycled asphalt RAP mixture and oil-loaded recycled particles at 120~140 ℃, so that the recycling agent is released through mesoporous channels and penetrates into the aged asphalt to regenerate it and obtain recycled mixture.

[0032] A4. Spread the above-mentioned recycled mixture at a travel speed of 4~5 m / min and compact it to complete the recycling of aged asphalt.

[0033] Compared with the prior art, the advantages of the present invention are as follows:

[0034] (1) This invention significantly reduces the regeneration temperature, energy consumption and carbon emissions, and the hollow mesoporous structure of the nanoparticles (pore size 2~5 nm) provides an ultra-large specific surface area (>600 m²). 2 / g), shortening the diffusion path of the rejuvenator to the micrometer level; the functionalized shell enhances the compatibility with aged asphalt, achieving efficient penetration at 120~140 ℃ (traditional processes require 160~180 ℃), reducing the aggregation of directly added rejuvenator in asphalt, enhancing the diffusion ability of the rejuvenator in aged asphalt, thereby improving its dispersion uniformity in the asphalt medium. After being transported through a nanocarrier, the rejuvenator can effectively depolymerize asphaltene aggregates and restore the colloidal structure of asphalt.

[0035] (2) This invention significantly improves construction speed and shortens the time to open to traffic. The recycler is intelligently released through mesoporous channels and can complete the penetration at low temperature. Combined with temperature-speed linkage control, it avoids the traditional process from being forced to slow down due to waiting for penetration. The on-site thermal recycling unit spreads the recycled mixture at a speed of 4~5 m / min (the on-site thermal recycling unit generally travels at a speed of 2.5~3.5 m / min when the traditional recycler is recycled).

[0036] (3) The regenerator of the present invention is intelligently released through mesoporous channels and can be fully penetrated at low temperatures; the shell structure of hollow mesoporous silica can partially block the intrusion of oxygen and ultraviolet rays, reduce the aging of asphalt, and delay the secondary aging of asphalt; enhance the high-temperature stability of asphalt and reduce the risk of rutting; wherein, the silanization modification of hollow mesoporous silica enhances the bonding force between the carrier and asphalt interface, enhances the high-temperature stability of asphalt, reduces the risk of rutting, delays the high-temperature decomposition of the regenerator, and delays the aging of asphalt; pyridine gradient functionalization can improve the anti-aging ability of asphalt.

[0037] (4) The ultra-low dosage of the present invention achieves high-performance regeneration, reduces the cost of the whole cycle, and reduces the dosage to 2-6% by the carrier oil loading rate of 320-370%, while the traditional on-site thermal regeneration dosage is generally above 8%. The oil loading is precisely controlled by changing the parameters of the formula. At the same time, the hollow mesoporous silica carrier characteristics enable the regenerator to continue to work at low temperature (-24 ℃~-28 ℃), inhibiting the glass transition of asphalt, thereby effectively reducing the amount of regenerator used, which is in line with the concept of green and sustainable development. Attached Figure Description

[0038] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0039] Figure 1 (a) and (b) are TEM images of hollow mesoporous silica prepared in Example 1 of the present invention;

[0040] Figure 2 (a) and (b) are SEM images of the hollow mesoporous silica prepared in Example 1 of the present invention;

[0041] Figure 3 Fluorescence spectra of functionalized hollow mesoporous silica oil-carrying regenerated particles prepared in Example 1 applied to regenerated asphalt; (a) shows the functionalized hollow mesoporous silica oil-carrying regenerated particles added to asphalt; (b) shows the regenerator directly added to asphalt. Detailed Implementation

[0042] Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the accompanying drawings are exemplary and intended to explain the present invention, and should not be construed as limiting the present invention.

[0043] It should be noted that the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. Furthermore, in the description of this invention, unless otherwise stated, "a plurality of" means two or more.

[0044] In this document, the terms “containing,” “comprising,” or “including” are open-ended expressions, meaning they include the contents specified in this invention but do not exclude other aspects.

[0045] In this document, the terms “optional,” “optionally,” or “optional” generally refer to an event or condition that may, but may not, occur, and the description includes both cases in which the event or condition occurs and cases in which the event or condition does not occur.

[0046] It should be noted that the regenerator of this invention is intelligently released through mesoporous channels (the release rate is 3 times faster than direct addition), and can complete penetration at low temperatures; the shell structure of hollow mesoporous silica can partially block the intrusion of oxygen and ultraviolet light, reducing asphalt aging and delaying secondary asphalt aging; the structure of hollow mesoporous silica can enhance the high-temperature stability of asphalt and reduce the risk of rutting. In contrast, traditional regenerators are prone to volatilization and loss when directly sprayed, while the regenerator of this invention, loaded in mesoporous silica, can be released slowly, reducing volatilization loss and improving utilization.

[0047] Meanwhile, KH-550 silanization modification of hollow mesoporous silica enables -NH2 to form hydrogen bonds with polar components of asphalt (such as asphaltenes), enhancing the bonding force between the carrier and asphalt interface, improving the high-temperature stability of asphalt, reducing the risk of rutting, and stabilizing the silane layer at 180 ℃, thus delaying the high-temperature decomposition of the regenerator and slowing down asphalt aging. Gradient functionalization of 4-pyridinecarboxylic acid enables π-π stacking of pyridine rings with aromatic components in the regenerator, achieving targeted slow release. Pyridine nitrogen atoms capture free radicals generated by ultraviolet aging, interrupting the oxidation chain reaction and improving the anti-aging ability of asphalt.

[0048] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the protection scope of the present invention.

[0049] Preferably, the present invention provides a method for preparing functionalized hollow mesoporous silica oil-loaded regenerated particles and its application method, specifically including the following steps:

[0050] Step 1: Preparation of nano-hollow mesoporous silica (HMSN) support by sacrificial template method;

[0051] (1) Mix 19 ml of deionized water with 8-10 ml of anhydrous ethanol, and adjust the pH to 11-13 with ammonia. Add 0.2 g of 3-aminophenol during stirring, and add formaldehyde solution at 80 °C to obtain a mixture and form phenolic resin microspheres.

[0052] (2) Add 0.9 g of surfactant to the above mixture, and then add triethanolamine (TEA) at a mass ratio of 10:1. Stir at 80 °C for 30 min, and then add 0.72~1.44 ml of silicon source and stir for 2~6 h. Centrifuge the above mixture, wash it three times with deionized water, dry it, and remove the surfactant to obtain nano-hollow mesoporous silica (HMSN).

[0053] (3) Place 5-10 g of the above HMSN into 50-100 mL of ethanol-water aqueous solution with a volume ratio of (3-5):1, stir at room temperature for 1-1.5 h, pour into a beaker, adjust the pH to 3-5 with HCl, add silane coupling agent to obtain a suspension, centrifuge, wash and dry to obtain HMSN with surface alkyl modification;

[0054] (4) Dissolve 0.5~2 g of 4-pyridinecarboxylic acid in 50~180 ml of PBS buffer (pH=7.2~7.4), and add 0.3~0.5 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC) and 0.2~0.4 g of N-hydroxysuccinimide (NHS). Stir at 20~25 °C for 2 h to activate the carboxyl group and obtain an activated solution. Then, put the HMSN with surface alkyl modification in step S4 into the above activated solution and react in the dark for 24~28 h to obtain a hollow mesoporous silica support with alkyl and pyridine group gradient modification.

[0055] Step 2: Preparation of functionalized hollow mesoporous silica oil-loaded regenerated particles by vacuum adsorption method;

[0056] (5) Prepare a mixture with a volume ratio of regenerator to anhydrous ethanol or ethyl acetate of 1.25:40, and stir at room temperature at a speed of 300 r / min to make the oil droplet molecules uniformly dispersed in the anhydrous ethanol;

[0057] (6) At 80°C, the hollow mesoporous silica support with alkyl and pyridine group gradient modification prepared in step 1 was incorporated into the above mixed solution, and stirred at low speed for 30 min under negative pressure, with a rotation speed of 600 r / min and an absolute value of vacuum pressure difference of 0.05~0.2 MPa.

[0058] (7) Repeat the above steps three times, filter with deionized water, dry at 50~80 ℃ for 6~8 h, so that the regenerator is adsorbed into the hollow cavity and mesoporous channels to obtain the functionalized hollow mesoporous silica oil-carrying regenerated particles.

[0059] Step 3: Application method of the above-mentioned oil-carrying regenerated particles;

[0060] (8) Milling the pavement with asphalt aging that has been in service for more than 5 years to obtain recycled asphalt RAP mixture; the aged asphalt meets the following requirements: penetration ≤ 40 (0.1 mm), softening point ≥ 55 ℃;

[0061] (9) The functionalized hollow mesoporous silica oil-loaded recycled particles are added to RAP at a dosage of 2-6% of the mass of RAP asphalt; the dosage of traditional in-situ thermal recycling is generally above 8%.

[0062] (10) Heat and mix RAP and oil-loaded regenerated particles at 120~140 ℃ to release the regenerator through mesoporous channels and penetrate into the aged asphalt to regenerate it;

[0063] (11) The recycled mixture is laid at a speed of 4~5 m / min using an on-site hot recycling unit and compacted at >110℃ to complete the recycling of aged asphalt.

[0064] Preferably, the method for removing surfactant in step (2) includes calcination, solvent extraction and chemical etching.

[0065] Preferably, the silicon source in step (2) includes one of tetraethyl orthosilicate (TEOS), methyltrimethoxysilane (MTMS), methyltriethoxysilane (MTES), 3-aminopropyltriethoxysilane (APTES), methyl orthosilicate, propyl orthosilicate, and butyl orthosilicate; the surfactant in step (2) includes one of hexadecyltrimethylammonium chloride (CTAC), hexadecyltrimethylammonium bromide (CTAB), hexadecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, and octadecyltrimethylammonium bromide; and the silane coupling agent in step (3) includes hexamethyldisilazane (HMDS), trimethylchlorosilane (TMCS), and octadecyltrimethoxysilane (ODS, C 18 H 37 One of Si(OCH3)3 and γ-aminopropyltriethoxysilane (KH-550).

[0066] Preferably, in step (3), the mass ratio of silane coupling agent to HMSN is (3-4):1; and in step (4), the mass ratio of 4-pyridinecarboxylic acid to surface-alkyl-modified HMSN is (0.3-0.5):1.

[0067] Preferably, in step 2, the mass ratio of the regenerator to the functionalized hollow mesoporous silica is (4-5):1.

[0068] Example 1

[0069] This embodiment provides a method for preparing functionalized hollow mesoporous silica oil-loaded regenerated particles and its application method, specifically including the following steps:

[0070] Step 1: Preparation of nano-hollow mesoporous silica (HMSN) support by sacrificial template method;

[0071] (1) 19 ml of deionized water and 8 ml of anhydrous ethanol were mixed, and ammonia was added to adjust the pH to 11. 0.2 g of 3-aminophenol was added during stirring, and a formaldehyde aqueous solution (formaldehyde concentration of 37 wt%) with a mass ratio of 3-aminophenol to formaldehyde of 1:1.5 was added at 80 °C to obtain a mixed solution and formaldehyde resin microspheres were formed.

[0072] (2) Add 0.9 g of 25 wt% hexadecyltrimethylammonium chloride solution, then add triethanolamine at a mass ratio of 10:1, stir at 80 ℃ for 30 min, add 0.72 ml tetraethyl orthosilicate and stir for 2 h, centrifuge and wash three times with deionized water, dry, then place the prepared particles in a muffle furnace and calcine at 550 ℃ for 6 h, cool and set aside to obtain nano-hollow mesoporous silica (HMSN);

[0073] This hollow mesoporous silica was observed using a transmission electron microscope, as shown below. Figure 1 As shown, the particles exhibit a distinct hollow structure, with a hollow cavity diameter of approximately 490 nm (accounting for about 84% of the total diameter), a shell thickness of approximately 46 nm, and uniformly distributed mesopores with a pore size of approximately 3.7 nm on the shell. Scanning electron microscopy reveals... Figure 2 As shown, HMSN particles are spherical with an average particle size of 582 nm and good dispersibility. The specific surface area of ​​HMSN was analyzed using an Omnisorp 100CX surface area analyzer, and the measured specific surface area was 746 m². 2 / g.

[0074] (3) Take 10 g of HMSN and add it to 100 ml of ethanol-water solution (volume ratio of ethanol to water is 3:1). Stir with a magnetic stirrer at room temperature for 1 h and pour it into a beaker. Adjust the pH to 3 with HCl water solution. Adjust the speed of the magnetic stirrer to 300 r / min. Add 30 g of KH-550 to the beaker at a mass ratio of HMSN to KH-550 of 1:3. Stir magnetically in an oil bath at 80℃ for 5 h to obtain a uniform suspension. After cooling to room temperature, centrifuge the obtained emulsion at 1000 r / min to remove the precipitate. Wash the precipitate twice or more with a mixture of ethanol and deionized water (volume ratio of 1:1). Then dry it in a vacuum drying oven at 60℃ for 5 h to obtain HMSN with alkyl surface modification (KH-550-HMSN).

[0075] (4) Dissolve 0.5 g of 4-pyridinecarboxylic acid in 50 ml of PBS buffer (pH=7.4), add 0.3 g of EDC and 0.2 g of NHS, stir at 25 °C for 2 h to activate the carboxyl group, add 1 g of KH-550-HMSN to the above activation solution, stir magnetically at 400 rpm at 25 °C for 24 h in the dark, then wash three times with deionized water and anhydrous ethanol respectively, and dry at 60 °C for 5 h to finally obtain a hollow mesoporous silica support modified with alkyl and pyridine groups.

[0076] Step 2: Preparation of functionalized hollow mesoporous silica oil-loaded regenerated particles by vacuum adsorption method;

[0077] (5) Prepare a mixture with a volume ratio of sunflower seed oil (purchased from Hebei Dingkang Grain and Oil Co., Ltd.) to anhydrous ethanol of 1.25:40, and stir at room temperature at a speed of 300 r / min to make the oil droplet molecules evenly dispersed in the anhydrous ethanol.

[0078] (6) At 80 °C, 1.2 g of the hollow mesoporous silica powder prepared in step 1 was added to the above mixed solution and stirred at low speed for 30 min under negative pressure. The rotation speed was 600 r / min and the absolute value of the vacuum pressure difference was 0.1 MPa. At this time, the mass ratio of hollow mesoporous silica to asphalt recycling agent was 1:4.5.

[0079] (7) Repeat the above steps three times, filter with deionized water, dry at 60 °C for 7 h, and the resulting yellow powder is the functionalized hollow mesoporous silica oil-loaded regenerated particles. The loading rate can reach 345% by TG / DSC characterization ([total mass loss of hollow mesoporous silica loaded regenerator at 0~1000 °C - mass loss of hollow mesoporous silica] / final remaining mass).

[0080] Based on the parameters of hollow mesoporous silica and the conditions of the loaded regenerator, the following formula is fitted:

[0081]

[0082] The parameters of the formula are: L oil Oil load factor, in %; ρ oil The density of the oil it carries is expressed in g / cm³. 3 V hollow The volume of the hollow cavity in the mesoporous silica is expressed in cm³. 3 / g;S meso This refers to the mesoporous specific surface area of ​​hollow mesoporous silica, in m³. 2 / g; This is the absolute value of the vacuum pressure difference, in MPa. This is the oil-carrier contact angle, in degrees (°). The viscosity is expressed as oil, in mPa·s. The particle packing porosity is 0.75.

[0083] According to the formula and the parameters in Example 1, L can be calculated. oil The oil load rate is 345%.

[0084] Step 3: Application method of the above-mentioned oil-carrying regenerated particles;

[0085] (8) Milling the asphalt pavement that has been in service for 5 years (taken from Wuhan-Huangshi Expressway) to obtain recycled asphalt RAP mixture. The aged asphalt meets the following requirements: penetration 32 (0.1 mm) and softening point 61.8 ℃.

[0086] (9) Add the oil-loaded recycled particles prepared in step 2 to the RAP at a dosage of 5% of the mass of the above-mentioned recycled asphalt RAP mixture;

[0087] (10) Heat and mix RAP and oil-loaded recycled particles at 120 °C to release the regenerator through mesoporous channels and penetrate into the aged asphalt to regenerate it;

[0088] (11) The recycled mixture is spread at a speed of 4 m / min using an on-site thermal recycling unit and compacted at 120°C to complete the recycling.

[0089] Example 2

[0090] This embodiment provides a method for preparing and applying functionalized hollow mesoporous silica oil-loaded regenerated particles (HMSNs). Different sizes of HMSNs are obtained by adjusting the pH value, silica source dosage, and stirring time. The specific steps include:

[0091] Step 1: Preparation of nano-hollow mesoporous silica (HMSN) support by sacrificial template method;

[0092] (1) 19 ml of deionized water and 8 ml of anhydrous ethanol were mixed, and ammonia was added to adjust the pH to 13. During the stirring process, 0.2 g of 3-aminophenol was added, and a formaldehyde aqueous solution (formaldehyde concentration of 37 wt%) with a mass ratio of 3-aminophenol to formaldehyde of 1:1.5 was added at 80 °C to obtain a mixed solution, and phenolic resin microspheres were formed.

[0093] (2) Add 0.9 g of 25 wt% hexadecyltrimethylammonium chloride solution, then add triethanolamine at a mass ratio of 10:1, stir at 80 ℃ for 30 min, add 1.44 ml of methyltriethoxysilane and stir for 6 h, centrifuge and wash three times with deionized water, dry, then place the prepared particles in a muffle furnace and calcine at 550 ℃ for 6 h, cool and set aside to obtain nano-hollow mesoporous silica (HMSN);

[0094] This hollow mesoporous silica has an average particle size of approximately 300 nm, a hollow cavity diameter of approximately 260 nm (accounting for approximately 87% of the total diameter), a shell thickness of approximately 20 nm, and mesopore diameters of approximately 2 nm. The specific surface area of ​​the HMSN was analyzed using an Omnisorp 100CX surface area analyzer, and the measured specific surface area was approximately 600 m². 2 / g.

[0095] (3) Take 5 g of HMSN and add it to 50 ml of ethanol-water solution (volume ratio of ethanol to water is 5:1). Stir with a magnetic stirrer at room temperature for 1.5 h and pour it into a beaker. Adjust the pH to 5 with HCl solution. Adjust the speed of the magnetic stirrer to 200 r / min. Add 20 g of KH-550 to the beaker at a mass ratio of HMSN to KH-550 of 1:4. Stir magnetically in an oil bath at 80℃ for 4 h to obtain a uniform suspension. After cooling to room temperature, centrifuge the obtained emulsion at 1200 r / min. Remove the precipitate by washing it more than twice with a mixture of ethanol and deionized water (volume ratio of 1:1). Then dry it in a vacuum drying oven at 60℃ for 5 h to obtain HMSN (KH-550-HMSN) with alkyl surface modification.

[0096] (4) Dissolve 0.3 g of 4-pyridinecarboxylic acid in 180 ml of PBS buffer (pH=7.2), add 0.5 g of EDC and 0.4 g of NHS, stir at 25 °C for 2 h to activate the carboxyl group, add 1 g of KH-550-HMSN to the above activation solution, stir magnetically at 400 rpm at 25 °C for 28 h in the dark, then wash three times with deionized water and anhydrous ethanol respectively, and dry at 60 °C for 5 h to finally obtain a hollow mesoporous silica support modified with alkyl and pyridine groups.

[0097] Step 2: Preparation of functionalized hollow mesoporous silica oil-loaded regenerated particles by vacuum adsorption method;

[0098] (5) Prepare a mixture with a volume ratio of sunflower seed oil to anhydrous ethanol of 1.25:40, and stir at room temperature at a speed of 300 r / min to make the oil droplet molecules evenly dispersed in the anhydrous ethanol.

[0099] (6) At 80 °C, 2 g of the hollow mesoporous silica powder prepared in step 1 was added to the above mixed solution and stirred at low speed for 30 min under negative pressure. The rotation speed was 600 r / min and the absolute value of the vacuum pressure difference was 0.05 MPa. At this time, the mass ratio of hollow mesoporous silica to asphalt recycling agent was 1:4.

[0100] (7) Repeat the above steps three times, filter with deionized water, dry at 60 °C for 7 h, and the resulting yellow powder is the functionalized hollow mesoporous silica oil-loaded regenerated particles.

[0101] Based on the parameters of hollow mesoporous silica and the conditions of the loaded regenerator, the following formula is fitted:

[0102]

[0103] The parameters of the formula are: L oil Oil load factor, in %; ρ oil The density of the oil it carries is expressed in g / cm³. 3 V hollow The volume of the hollow cavity in the mesoporous silica is expressed in cm³. 3 / g;S meso This refers to the mesoporous specific surface area of ​​hollow mesoporous silica, in m³. 2 / g; This is the absolute value of the vacuum pressure difference, in MPa. This is the oil-carrier contact angle, in degrees (°). The viscosity is expressed as oil, in mPa·s. The particle packing porosity is 0.75.

[0104] According to the formula and the parameters in Example 2, L can be calculated. oil The oil load rate is 320%.

[0105] Step 3: Application method of the above-mentioned oil-carrying regenerated particles;

[0106] (8) Milling the asphalt-aged pavement that has been in service for 5 years to obtain recycled asphalt RAP mixture, wherein the aged asphalt meets the following requirements: penetration 32 (0.1 mm) and softening point 61.8 ℃;

[0107] (9) Add the oil-loaded recycled particles prepared in step 2 to the RAP at a dosage of 6% of the mass of the above-mentioned recycled asphalt RAP mixture;

[0108] (10) Heat and mix RAP and oil-loaded recycled particles at 140 °C to release the regenerator through mesoporous channels and penetrate into the aged asphalt to regenerate it;

[0109] (11) The recycled mixture is spread at a speed of 4 m / min using an on-site thermal recycling unit and compacted at 120°C to complete the recycling.

[0110] Example 3

[0111] This embodiment provides a method for preparing and applying functionalized hollow mesoporous silica oil-loaded regenerated particles (HMSNs). By adjusting the amount of anhydrous ethanol, HMSNs of different sizes were obtained. The specific steps include:

[0112] Step 1: Preparation of nano-hollow mesoporous silica (HMSN) support by sacrificial template method;

[0113] (1) 19 ml of deionized water and 10 ml of anhydrous ethanol were mixed, and ammonia was added to adjust the pH to 11. 0.2 g of 3-aminophenol was added during stirring, and a formaldehyde aqueous solution (formaldehyde concentration of 37 wt%) with a mass ratio of 3-aminophenol to formaldehyde of 1:1.5 was added at 80 °C to obtain a mixed solution and formaldehyde resin microspheres were formed.

[0114] (2) Add 0.9 g of 25 wt% hexadecyltrimethylammonium chloride solution, then add triethanolamine at a mass ratio of 10:1, stir at 80 ℃ for 30 min, add 0.72 ml tetraethyl orthosilicate and stir for 2 h, centrifuge and wash three times with deionized water, dry, then place the prepared particles in a muffle furnace and calcine at 550 ℃ for 6 h, cool and set aside to obtain nano-hollow mesoporous silica (HMSN);

[0115] This hollow mesoporous silica has an average particle size of approximately 1110 nm, a hollow cavity diameter of approximately 910 nm (accounting for approximately 82% of the total diameter), a shell thickness of approximately 100 nm, and mesopore diameters of approximately 5 nm. The specific surface area of ​​the HMSN was analyzed using an Omnisorp 100CX surface area analyzer, and the measured specific surface area was approximately 1200 m². 2 / g.

[0116] (3) Take 10 g of HMSN and add it to 50 ml of ethanol-water solution (the volume ratio of ethanol to water is 3:1). Stir with a magnetic stirrer at room temperature for 1 h and pour it into a beaker. Adjust the pH to 3 with HCl water solution. Adjust the speed of the magnetic stirrer to 200 r / min. Add 30 g of KH-550 to the beaker at a mass ratio of HMSN to KH-550 of 1:3. Stir magnetically in an oil bath at 80 ℃ for 4 h to obtain a uniform suspension. After cooling to room temperature, centrifuge the obtained emulsion at 1000 r / min to remove the precipitate. Wash the precipitate more than twice with a mixture of ethanol and deionized water (volume ratio of 1:1). Then dry it in a vacuum drying oven at 60 ℃ for 5 h to obtain HMSN with alkyl surface modification (KH-550-HMSN).

[0117] (4) Dissolve 0.5 g of 4-pyridinecarboxylic acid in 50 ml of PBS buffer (pH=7.4), add 0.3 g of EDC and 0.2 g of NHS, stir at 25 °C for 2 h to activate the carboxyl group, add 1 g of KH-550-HMSN to the above activation solution, stir magnetically at 400 rpm at 25 °C for 28 h in the dark, then wash three times with deionized water and anhydrous ethanol respectively, and dry at 60 °C for 5 h to finally obtain a hollow mesoporous silica support modified with alkyl and pyridine groups.

[0118] Step 2: Preparation of functionalized hollow mesoporous silica oil-loaded regenerated particles by vacuum adsorption method;

[0119] (5) Prepare a mixture with a volume ratio of sunflower seed oil to anhydrous ethanol of 1.25:40, and stir at room temperature at a speed of 300 r / min to make the oil droplet molecules evenly dispersed in the anhydrous ethanol.

[0120] (6) At 80 °C, 1.2 g of the hollow mesoporous silica powder prepared in step 1 was added to the above mixed solution and stirred at low speed for 30 min under negative pressure. The rotation speed was 600 r / min and the absolute value of the vacuum pressure difference was 0.2 MPa. At this time, the mass ratio of hollow mesoporous silica to asphalt recycling agent was 1:5.

[0121] (7) Repeat the above steps three times, filter with deionized water, dry at 60 °C for 7 h, and the resulting yellow powder is the functionalized hollow mesoporous silica oil-loaded regenerated particles.

[0122] Based on the parameters of hollow mesoporous silica and the conditions of the loaded regenerator, the following formula is fitted:

[0123]

[0124] The parameters of the formula are: L oil Oil load factor, in %; ρ oil The density of the oil it carries is expressed in g / cm³. 3 V hollow The volume of the hollow cavity in the mesoporous silica is expressed in cm³. 3 / g;S meso This refers to the mesoporous specific surface area of ​​hollow mesoporous silica, in m³. 2 / g; This is the absolute value of the vacuum pressure difference, in MPa. This is the oil-carrier contact angle, in degrees (°). The viscosity is expressed as oil, in mPa·s. The particle packing porosity is 0.75.

[0125] According to the formula and the parameters in Example 3, L can be calculated. oil The oil load rate is 370%.

[0126] Step 3: Application method of the above-mentioned oil-carrying regenerated particles;

[0127] (8) Milling the asphalt-aged pavement that has been in service for 5 years to obtain recycled asphalt RAP mixture, wherein the aged asphalt meets the following requirements: penetration 32 (0.1 mm) and softening point 61.8 ℃;

[0128] (9) Add the oil-loaded recycled particles prepared in step 2 to the RAP at a dosage of 2% of the mass of the above-mentioned recycled asphalt RAP mixture;

[0129] (10) Heat and mix RAP and oil-loaded recycled particles at 140 °C to release the regenerator through mesoporous channels and penetrate into the aged asphalt to regenerate it;

[0130] (11) The recycled mixture is spread at a speed of 5 m / min using an on-site thermal recycling unit and compacted at 120 ℃ to complete the recycling.

[0131] Example 4

[0132] This embodiment provides a method for preparing functionalized hollow mesoporous silica oil-carrying regenerated particles and its application method. The difference from Embodiment 1 is that in step 2, when preparing functionalized hollow mesoporous silica oil-carrying regenerated particles, furfural, a petroleum-based regenerator with poor permeability, is used as the regenerator to extract oil. The rest is the same as in Embodiment 1.

[0133] Example 5

[0134] This embodiment provides a method for preparing functionalized hollow mesoporous silica oil-loaded regenerated particles and its application method. The difference from Embodiment 1 is that in the application method of step 3, the amount of oil-loaded regenerated particles is 3% of the RAP content, and the rest is the same as in Embodiment 1.

[0135] Example 6

[0136] This embodiment provides a method for preparing functionalized hollow mesoporous silica oil-loaded regenerated particles and its application method. The difference from Embodiment 1 is that in the application method of step 3, the amount of oil-loaded regenerated particles is 4% of the RAP content, and the rest is the same as in Embodiment 1.

[0137] Example 7

[0138] This embodiment provides a method for preparing functionalized hollow mesoporous silica oil-loaded regenerated particles and its application method. The difference from Embodiment 1 is that in the application method of step 3, the amount of oil-loaded regenerated particles is 6% of the RAP content, and the rest is the same as in Embodiment 1.

[0139] To compare the effects of surface modification of nano-hollow mesoporous silica, the effects of light oil regenerators with different wettability on oil loading, and the effects of oil-loaded regenerating particle dosage on RAP regeneration performance, the following comparisons were also made.

[0140] Comparative Example 1

[0141] This comparative example provides a method for preparing and applying ordinary hollow mesoporous silica oil-loaded regenerated particles. The difference from Example 1 is that no functional modification is performed on the nano-mesoporous silica, that is, steps (3) and (4) in Example 1 are cancelled, while the rest is the same as Example 1.

[0142] Comparative Example 2

[0143] This comparative example provides a method for preparing and applying hollow mesoporous silica-loaded light oil regenerated particles. The difference from Example 1 is that in step 2, castor oil is used as the regenerating agent when preparing hollow mesoporous silica-loaded light oil regenerated particles. The rest is the same as in Example 1.

[0144] Comparative Example 3

[0145] This comparative example provides a method for directly regenerating aged asphalt without oil loading. The difference is that 10% of the regenerator is directly added for regeneration, that is, in step 3, sunflower seed oil with a dosage of 10% of the RAP content is directly added.

[0146] Comparative Example 4

[0147] This comparative example provides a method for preparing and applying silane-modified hollow mesoporous silica oil-carrying regenerated particles. The difference from Example 1 is that only siloxane modification is performed on the nano-hollow mesoporous silica to obtain alkyl-modified hollow mesoporous silica, that is, step (3) in Example 1 is omitted, and the rest is the same as Example 1.

[0148] The regeneration effect of the functionalized hollow mesoporous silica oil-loaded regenerated particles prepared in this invention on RAP recycled materials has not been verified. The above examples and comparative examples were tested for high-temperature rutting dynamic stability (T 0719—2011) and low-temperature beam bending failure strain (GB / T 38948-2020), respectively. The results are shown in Table 1.

[0149]

[0150] As shown in the table, the high and low temperature performance of asphalt mixtures can be significantly restored after regeneration of RAP recycled material by adding the nano-hollow mesoporous silica composite regenerator of this invention. Based on the high-temperature rutting dynamic stability and low-temperature beam bending failure strain of Examples 1, 5, 6, and 7, it can be seen that a regenerator content of 3-6% can restore the performance of RAP recycled mixtures to normal levels. Comparing Examples 5 and 6, it can be found that when 3% composite regenerator is added, the high-temperature performance of the asphalt mixture has been restored. Further increasing the composite regenerator dosage does not significantly change the high and low temperature performance, indicating that the nano-hollow mesoporous silica in the composite regenerator has a slow-release effect on the regenerator. In Example 2, different silicon sources were used to prepare nano-silica carriers, and the results showed that the type of silicon source had no significant effect on the regenerator loading rate. Example 4 illustrates the difference in oil loading rates of the nanoporous silica carrier due to the differences in consistency, density, and other properties of different types of light oil rejuvenators. The oil loading rate in Example 1 was 345%, while that in Example 4 was 330%, a difference of only 15%, demonstrating that the nanoporous silica described in this invention has excellent compatibility with different types of asphalt rejuvenators. Example 3 showed the best recovery of high and low temperature properties in the recycled asphalt mixture, indicating that the size of the nanoporous silica can be controlled by changing the size of the template, thereby achieving controllable adjustment of the rejuvenator loading rate and release rate, accelerating the release speed of the rejuvenator, and thus accelerating the regeneration rate.

[0151] In Comparative Example 1, without functional modification of the nanoporous silica, the oil loading rate of the carrier was only 200%, indicating that surface modification of the hollow mesoporous silica can significantly improve the compatibility between the carrier and the regenerant, and increase the loading rate of the regenerant. However, siloxane modification of the hollow mesoporous silica alone increased the oil loading by 40% compared to the unmodified version, a negligible improvement. In Comparative Example 3, instead of using nanoporous silica as a carrier, a large amount of regenerant was added. It was found that the regenerant had poor dispersibility during the asphalt mixture mixing process. The regeneration results showed that the high and low temperature performance of the regenerated asphalt mixture could not be restored to normal levels, which was worse than the regeneration effect achieved by using hollow mesoporous silica-loaded regenerant in Example 1. In Comparative Example 2, castor oil was used for regeneration. The loading rate was significantly lower than that in Example 1 because castor oil contains 90% ricinoleic acid, which has a large molecular weight and higher viscosity. This results in greater diffusion resistance within the nanopores, leading to a decrease in oil loading efficiency. Castor oil contains hydroxyl groups, which are highly polar and have weak bonding with the alkyl chains of modified HMSN, thus reducing interfacial adsorption capacity. Furthermore, the hydroxyl structure of castor oil easily forms intermolecular hydrogen bonds within the mesopores, causing oil molecules to aggregate and hindering cavity filling.

[0152] To verify the release effect of the hollow mesoporous silica regenerator in this invention, the inventors labeled the regenerator with β-carotene, and then loaded it onto hollow mesoporous silica, obtaining the following results. Figure 3 As shown, it can be seen by fluorescence microscopy, Figure 3 (a) shows the addition of functionalized hollow mesoporous silica oil-carrying regenerated particles to asphalt. It can be seen that the particles are uniformly dispersed in the asphalt without agglomeration. Figure 3 In (b), the rejuvenator is directly added to the asphalt. It can be seen that the rejuvenator is unevenly dispersed and only a small area contains the rejuvenator. Therefore, the hollow mesoporous silica rejuvenator can not only improve the segregation of asphalt and rejuvenator and make them evenly dispersed, but also reduce the loss of rejuvenator during the addition process and improve its utilization rate.

[0153] The embodiments described above are some, but not all, of the embodiments of the present invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

Claims

1. A functionalized hollow mesoporous silica oil-loaded regenerative particle, characterized in that, The functionalized hollow mesoporous silica is prepared by the following steps: S1, mixing deionized water and ethanol, adjusting pH, adding 3-aminophenol during stirring, adding formaldehyde solution to obtain a mixed solution, and forming phenolic resin microspheres; S2, adding a surfactant, triethanolamine and a silicon source to the mixed solution and stirring; S3, centrifuging, washing, drying and removing the surfactant to obtain hollow mesoporous silica particles; S4, stirring the hollow mesoporous silica particles in an ethanol aqueous solution, adjusting pH, and adding a silane coupling agent to obtain a suspension, which is centrifuged, washed and dried to obtain the surface alkyl-modified hollow mesoporous silica; S5, dissolving 4-picolinic acid in a buffer solution, adding 1-ethyl-carbodiimide hydrochloride and N-hydroxysuccinimide to obtain an activated solution, and then putting the surface alkyl-modified hollow mesoporous silica from step S4 into the activated solution to react in the dark to obtain the alkyl and pyridine group gradient-modified functionalized hollow mesoporous silica. In step S4, the mass ratio of the silane coupling agent to the hollow mesoporous silica particles is (3-4):1; and in step S5, the mass ratio of 4-picolinic acid to the surface alkyl-modified hollow mesoporous silica particles is (0.3-0.5):

1. In step S2, the silicon source includes one of tetraethyl orthosilicate, methyltrimethoxysilane, methyltriethoxysilane, 3-aminopropyl triethoxysilane, methyl orthosilicate, propyl orthosilicate and butyl orthosilicate; in step S3, the surfactant includes one of cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide and octadecyltrimethylammonium bromide; and in step S4, the silane coupling agent includes one of hexamethyldisilazane, trimethylchlorosilane, octadecyltrimethoxysilane and γ-aminopropyl triethoxysilane.

2. The functionalized hollow mesoporous silica support oil regen eration particles according to claim 1, characterized in that, The hollow mesoporous silica has a particle size of 300-1110 nm, a pore size of mesoporous channels of 2-5 nm, a shell thickness of 20-100 nm, and a specific surface area of 600-1200 m 2 / g, and the hollow cavity accounts for 82%-87% of the particle diameter.

3. The functionalized hollow mesoporous silica support oil-regeneration particle of claim 1, wherein, The preparation method of the functionalized hollow mesoporous silica oil-loaded regeneration particle includes the following steps: adding a regeneration agent and a functionalized hollow mesoporous silica into a solvent, mixing and stirring under negative pressure, the absolute value of the vacuum pressure difference is 0.05-0.2 Mpa, and drying after vacuum adsorption to obtain the functionalized hollow mesoporous silica oil-loaded regeneration particle.

4. The functionalized hollow mesoporous silica support oil regen eration particles according to claim 1, wherein, The oil loading capacity of the hollow mesoporous silica is calculated by the following formula: The preparation method of the functionalized hollow mesoporous silica oil-loaded regeneration particle includes the following steps: adding a regeneration agent and a functionalized hollow mesoporous silica into a solvent, mixing and stirring under negative pressure, the absolute value of the vacuum pressure difference is 0.05-0.2 Mpa, and drying after vacuum adsorption to obtain the functionalized hollow mesoporous silica oil-loaded regeneration particle. ； Wherein, the parameters of each term of the formula are: L oil is the oil loading rate, with a unit of %; p oil is the density of the loaded oil, with a unit of g / cm 3 ; V hollow is the hollow cavity volume of the hollow mesoporous silica, with a unit of cm 3 / g; S meso is the mesoporous specific surface area of the hollow mesoporous silica, with a unit of m 2 / g; is the absolute value of the vacuum pressure difference, with a unit of MPa; θ is the oil-carrier contact angle, with a unit of °; is the oil viscosity, with a unit of mPa·s; φ is the particle packing porosity, which is 0.

75.

5. A process for the preparation of the functionalized hollow mesoporous silica support oil-loaded regenerated particles according to any one of claims 1 to 4, characterized in that, The mass ratio of the regeneration agent to the functionalized hollow mesoporous silica is (4-5):

1.

6. The production method according to claim 5, characterized by, ​ 7. Use of the functionalized hollow mesoporous silica oil-loaded regenerated particles according to any one of claims 1 to 4, characterized in that, The functionalized hollow mesoporous silica oil-loaded regeneration particles are suitable for scenarios including asphalt pavement hot in-place recycling, asphalt pavement hot plant recycling, asphalt pavement cold plant recycling, asphalt pavement cold in-place recycling and asphalt pavement full-depth recycling.

8. A method of using the functionalized hollow mesoporous silica support oil regeneration particles according to any one of claims 1 to 4, characterized in that, The method comprises the following steps: A1, milling and planing the aged asphalt pavement to obtain a recycled asphalt RAP mixture; A2, adding the functionalized hollow mesoporous silica oil-loaded regeneration particles to the recycled asphalt RAP mixture at a mixing amount of 2-6% of the mass of the recycled asphalt RAP mixture; A3, heating and mixing the recycled asphalt RAP mixture and the oil-loaded regeneration particles at 120-140 DEG C, so that the regeneration agent is released through the mesoporous channels and penetrates into the aged asphalt, thereby regenerating the aged asphalt to obtain a regenerated mixture; A4, paving and compacting the regenerated mixture at a travel speed of 4-5 m / min, thereby completing the regeneration of the aged asphalt.

Images