Asphalt smoke suppressant for roads, smoke suppressant asphalt and preparation method

Abstract

The present invention relates to a road asphalt smoke suppressant, smoke suppressant asphalt and a preparation method. The preparation method of the road asphalt smoke suppressant includes the steps of: S1, blending zirconium oxychloride octahydrate with terephthalic acid and grinding to obtain a solid-solid blend; S2, adding N,N-dimethylformamide to the solid-solid blend and stirring at a constant temperature to dissolve the solid-solid blend to obtain a mixed solution; S3, transferring the mixed solution into a reactor and adding an acidic modulator to form a reaction system, and allowing the reaction system to undergo a hydrothermal reaction; S4, standing for a period of time after the reaction to obtain a reaction solid product, and washing and drying the reaction solid product to obtain a metal organic framework-based asphalt smoke suppressant with a three-dimensional network structure. The preparation method has a simple process, low cost, good compatibility with petroleum asphalt, can effectively suppress harmful exhaust gas generated by heating asphalt, and has good universality for smoke suppression.

Description

Technical Field

[0001] The invention belongs to the technical field of preparation of functional asphalt pavement materials, and in particular relates to an asphalt smoke suppressant for roads, smoke suppressant asphalt and a preparation method. Background Art

[0002] Asphalt pavement has the advantages of high driving comfort, low noise and easy maintenance, and has become a widely used paving form. Due to the high viscosity of asphalt binder at room temperature, hot mix asphalt (HMA) is often used in asphalt pavement construction. However, asphalt will produce a large amount of harmful exhaust gas during high-temperature heating, which will cause harmful gas exposure to workers in various links of the asphalt pavement construction process. The exhaust gas will also produce secondary organic aerosols when it is discharged into the atmosphere, which will seriously harm the surrounding environment.

[0003] Asphalt smoke suppressants can reduce the generation of harmful fumes during asphalt heating, mixing and paving, reduce the exposure of road workers and surrounding residents to harmful asphalt fumes, and achieve low-impact and green construction of road infrastructure.

[0004] The main principles of asphalt smoke suppressants can be divided into physical adsorption and chemical bonding. Physical adsorption is universally applicable, and the attraction between the adsorbent and asphalt smoke is mainly caused by van der Waals forces. Physical adsorbents adsorb target substances to their surfaces by providing adsorption sites on the surface. The attraction of these adsorption sites keeps the adsorbed molecules or ions near the adsorbent surface. Chemical smoke suppressants inhibit or slow down specific chemical processes by changing or hindering the progress of chemical reactions. Chemical inhibitors react chemically with target compounds to form new compounds or affect the rate of target reactions.

[0005] At present, asphalt smoke suppressants include inorganic powder chemical smoke suppressants and porous adsorption smoke suppressants. CN102604396A and CN115677266A use metal hydroxides (calcium hydroxide, magnesium hydroxide, aluminum hydroxide, copper hydroxide, iron hydroxide) and layered silicates to form inorganic powder chemical smoke suppressants. However, the smoke suppressants have poor compatibility with asphalt and have a density (about 2-5g / cm 3 ) is greater than the density of petroleum asphalt (about 1g / cm 3 ), when mixed with petroleum asphalt, it will sink to the bottom of the petroleum asphalt. When the petroleum asphalt is heated to produce smoke, the smoke will escape upward, and the inorganic powder chemical smoke suppressant is difficult to exert its smoke suppression effect. CN105199409A uses zeolite, diatomaceous earth, pumice, graphite, carbon nanotubes and titanium dioxide to prepare a porous adsorption smoke suppressant with a specific surface area of ​​380m 2 / g, but the weight ratio of the smoke suppressant in asphalt is 2%-10%, which is costly.

[0006] Therefore, existing asphalt smoke suppressants have problems such as poor compatibility with petroleum asphalt, severe segregation, poor universality for smoke suppression, and high cost. Summary of the invention

[0007] In order to solve the above problems existing in the prior art, the present invention provides a road asphalt smoke suppressant, smoke suppressant asphalt and a preparation method. The technical problem to be solved by the present invention is achieved by the following technical solutions:

[0008] The embodiment of the present invention provides a method for preparing an asphalt smoke suppressant for roads, comprising the steps of:

[0009] S1, blending zirconium oxychloride octahydrate and terephthalic acid and grinding to obtain a solid-solid blend;

[0010] S2, adding N,N-dimethylformamide to the solid-solid blend and stirring at a constant temperature to dissolve the solid-solid blend to obtain a mixed solution;

[0011] S3, transferring the mixed solution into a reaction kettle and adding an acidic modulator to form a reaction system, and subjecting the reaction system to a hydrothermal reaction;

[0012] S4. After the reaction is completed, the reaction is allowed to stand for a period of time to obtain a solid product, and the solid product is cleaned and dried to obtain a metal organic framework-based asphalt smoke suppressant with a three-dimensional network structure.

[0013] In one embodiment of the present invention, step S1 comprises:

[0014] The zirconium oxychloride octahydrate and the terephthalic acid in a mass ratio of 1:(1-2) are blended at 5°C-40°C and ground for 15min-30min to obtain the solid-solid blend.

[0015] In one embodiment of the present invention, step S2 comprises:

[0016] Adding the N,N-dimethylformamide to the solid-solid blend, and stirring at a constant temperature of 45° C. to 85° C. for 1 h to 3 h to dissolve the solid-solid blend, thereby obtaining the mixed solution;

[0017] Wherein, the mass ratio of the solid-solid blend to the N,N-dimethylformamide is 1:(100-200).

[0018] In one embodiment of the present invention, step S3 includes:

[0019] Transferring the mixed solution into a high-pressure reactor or a hydrothermal reactor, and adding an acidic modulator to form a reaction system, wherein the mass ratio of the acidic modulator to the mixed solution is 1:(3-5);

[0020] The reaction system is subjected to a hydrothermal reaction at 80°C-140°C for a reaction time of 10h-30h.

[0021] In one embodiment of the present invention, step S4 includes:

[0022] After the reaction is completed, the solid product is allowed to stand for 8 hours to 24 hours, and the solid product is taken out and washed alternately with ethanol and deionized water for 2 to 4 times;

[0023] The cleaned reaction solid product is dried in a vacuum drying oven at 70° C. to 110° C. for 10 h to 24 h to obtain the metal organic framework-based asphalt smoke suppressant.

[0024] In one embodiment of the present invention, the acidic modulator includes one or more of an inorganic acid modulator and an organic acid modulator; wherein,

[0025] The inorganic acid modulator includes one or more of concentrated hydrochloric acid, dilute hydrochloric acid, hydrofluoric acid, and concentrated sulfuric acid;

[0026] The organic acid modulator includes one or more of acetic acid, formic acid and benzoic acid.

[0027] In one embodiment of the present invention, when the acidic modulator is an inorganic acid modulator, the crystal form of the metal organic framework-based asphalt smoke suppressant is a spherical crystal form, the particle size is 50nm-150nm, and the specific surface area is 600m 2 / g-900m 2 / g;

[0028] When the acidic modulator is an organic acid modulator, the metal organic framework-based asphalt smoke suppressant has a regular octahedral crystal form, a particle size of 200nm-500nm, and a specific surface area of ​​900m 2 / g-1300m 2 / g.

[0029] Another embodiment of the present invention provides an asphalt smoke suppressant for roads, which is prepared by the preparation method of the asphalt smoke suppressant for roads described in the above embodiment, and the asphalt smoke suppressant is a metal organic framework-based asphalt smoke suppressant with a three-dimensional network structure.

[0030] Another embodiment of the present invention provides a method for preparing smoke-suppressing asphalt for roads, comprising the steps of:

[0031] Take 1 part of asphalt at 120°C-150°C, add 0.005-0.015 parts of the metal organic framework-based asphalt smoke suppressant as described in the above embodiment and stir to obtain smoke suppressant asphalt.

[0032] Another embodiment of the present invention provides a road smoke suppressant asphalt, which is prepared by the preparation method of road smoke suppressant asphalt described in the above embodiment, and includes: 1 part of asphalt and 0.005-0.015 parts of metal organic framework-based asphalt smoke suppressant.

[0033] Compared with the prior art, the present invention has the following beneficial effects:

[0034] 1. The preparation method of the present invention uses terephthalic acid, zirconium oxychloride octahydrate and an acidic modulator as raw materials to synthesize a metal organic framework-based asphalt smoke suppressant, which has a simple process and low cost. The zirconium oxychloride octahydrate forms zirconium oxygen clusters through hydrolysis and polymerization, and the carboxyl group of terephthalic acid is deprotonated to form terephthalate radicals. The terephthalate radicals are coordinated with the zirconium oxygen clusters to form zirconium-carboxylic acid coordination bonds, and the zirconium oxygen clusters are used as nodes and the terephthalate radicals are used as bridging ligands to assemble into a three-dimensional network structure, which has good compatibility with petroleum asphalt and avoids serious segregation. At the same time, the three-dimensional network structure is an ultra-porous structure with a high specific surface area, which can effectively suppress harmful exhaust gas generated by heating asphalt. Due to the "maze effect" caused by the porous structure, the harmful smoke of asphalt can be sealed and confined for a long time, which has a good odor-removing and smoke-suppressing effect, and has a good effect on VOCs and H 2 S, CO, SO 2 It can achieve high efficiency suppression of NO and has good universality in smoke suppression, which is conducive to the low carbonization, environmental protection and low harm of asphalt pavement.

[0035] 2. The preparation method of the present invention adds an acidic modulator to the reaction system. The acidic modulator molecules can affect the hydrolysis of zirconium and the coordination of zirconium oxygen clusters in the process of assembling into a three-dimensional network structure, thereby affecting the orderliness and defects of the three-dimensional network structure. Asphalt smoke suppressants prepared from different types of acidic substances have different physical and chemical properties and can achieve different smoke suppression performances. Therefore, the smoke suppressant prepared by this preparation method can be suitable for different types of asphalt, broadening the application scenarios of metal-organic framework-based asphalt smoke suppressants and improving the universality of metal-organic framework-based asphalt smoke suppressants. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 A schematic flow chart of a method for preparing a road asphalt smoke suppressant provided by an embodiment of the present invention;

[0037] Figure 2a-2f Microscopic morphology of the asphalt smoke suppressant provided for this embodiment and comparative example. DETAILED DESCRIPTION

[0038] The present invention is further described in detail below with reference to specific embodiments, but the embodiments of the present invention are not limited thereto.

[0039] Embodiment 1

[0040] See also Figure 1 , Figure 1 A schematic flow chart of a method for preparing a road asphalt smoke suppressant provided by an embodiment of the present invention. The preparation method comprises the following steps:

[0041] S1. Blending zirconium oxychloride octahydrate with terephthalic acid and grinding the mixture to obtain a solid-solid blend.

[0042] Specifically, zirconium oxychloride octahydrate and terephthalic acid in a mass ratio of 1:(1-2) are blended at 5°C-40°C, and fully ground in a mortar for 15min-30min to obtain a solid-solid blend.

[0043] Among them, zirconium oxychloride octahydrate is directly blended with terephthalic acid, and there is no requirement for the addition form and addition rate of the raw materials. The blending temperature is preferably 25°C.

[0044] S2. Add N,N-dimethylformamide to the solid-solid blend and stir at a constant temperature to dissolve the solid-solid blend to obtain a mixed solution.

[0045] Specifically, N,N-dimethylformamide is added to the solid-solid blend, and a constant temperature magnetic stirrer is used to stir the solid-solid blend at 45° C.-85° C. for 1 h-3 h, and the solid-solid blend is fully stirred to dissolve to obtain a mixed solution.

[0046] The mass ratio of the solid-solid blend to N,N-dimethylformamide is 1:(100-200). The constant temperature stirring temperature is preferably 60° C., and the stirring time is preferably 1 h.

[0047] S3. Transfer the mixed solution into a reaction kettle and add an acidic modulator to form a reaction system, and allow the reaction system to undergo a hydrothermal reaction.

[0048] Specifically, the mixed solution is first transferred into a high pressure reactor or a hydrothermal reactor, and an acidic modulator is added to form a reaction system. Then, the reaction system is subjected to a hydrothermal reaction at 80° C. to 140° C. for 10 h to 30 h.

[0049] The mass ratio of the acidic modulator to the mixed solution is 1:(3-5). The hydrothermal reaction temperature is preferably 120°C, and the reaction time is preferably 20 hours. The acidic modulator is added by direct blending, and there is no requirement for the addition form and addition rate.

[0050] In a specific implementation, the acidic modulator includes one or more of an inorganic acid modulator and an organic acid modulator. The inorganic acid modulator includes one or more of concentrated hydrochloric acid, dilute hydrochloric acid, hydrofluoric acid, and concentrated sulfuric acid, and the organic acid modulator includes one or more of acetic acid, formic acid, and benzoic acid.

[0051] In this embodiment, the hydrothermal reaction process of terephthalic acid, zirconium oxychloride octahydrate and acidic modifier as raw materials is as follows: zirconium oxychloride octahydrate undergoes hydrolysis reaction in N,N-dimethylformamide, and the generated hydroxy zirconium ions further polymerize to form zirconium oxy clusters. The carboxyl group of terephthalic acid is deprotonated to form terephthalate, which coordinates with zirconium oxygen clusters to form zirconium-carboxylic acid coordination bonds. The zirconium oxygen clusters serve as nodes and the terephthalate as bridging ligands to assemble into a three-dimensional network structure.

[0052] In the process of assembling into a three-dimensional network structure, the acidic regulator molecules may affect the hydrolysis of zirconium and the coordination of zirconium oxygen clusters, thereby affecting the orderliness and defects of the three-dimensional network structure. For inorganic acid modulators, on the one hand, they can inhibit the excessive hydrolysis of zirconium, lower the pH value of the solution, reduce the degree of hydrolysis of zirconium ions, and prevent the formation of excessive precipitation; on the other hand, they can accelerate the nucleation rate, promote the orderly growth of crystals, and obtain products with higher crystallinity. For organic acid modulators, the carboxyl group of the organic acid can react with the zirconium oxygen clusters. Coordination, temporarily occupying part of the coordination sites, delaying the coordination of terephthalate, and controlling the crystal growth rate; by adding organic acid regulators, structural defects can be introduced, the porosity can be increased, the particle size can be improved, and the performance of the material can be improved.

[0053] S4. After the reaction is completed, the reaction is allowed to stand for a period of time to obtain a solid product, and the solid product is cleaned and dried to obtain a metal organic framework-based asphalt smoke suppressant with a three-dimensional network structure.

[0054] Specifically, after the reaction is completed, the reaction mixture is allowed to stand for 8h-24h, the reaction solid product is taken out, and the reaction solid product is washed alternately with ethanol and deionized water for 2-4 times; then, the washed reaction solid product is dried in a vacuum drying oven at 70°C-110°C for 10h-24h to obtain a metal organic framework-based asphalt smoke suppressant.

[0055] Specifically, when the acidic modulator uses different types of acidic substances, the metal organic framework-based asphalt smoke suppressant has different crystal forms, particle sizes and specific surface areas, thereby achieving different smoke suppression properties of the metal organic framework-based asphalt smoke suppressant.

[0056] In a specific embodiment, when the acidic modulator is an inorganic acid modulator, the crystal form of the metal organic framework-based asphalt smoke suppressant is a spherical crystal form, the particle size is 50nm-150nm, and the specific surface area is 600m2 / g-900m 2 When the acid modulator is an organic acid modulator, the crystal form of the metal organic framework-based asphalt smoke suppressant is a regular octahedral crystal form, the particle size is 200nm-500nm, and the specific surface area is 900m 2 / g-1300m 2 / g.

[0057] The preparation method of the present invention adds an acidic modulator into the reaction system. The acidic modulator molecules can affect the hydrolysis of zirconium and the coordination of zirconium oxygen clusters in the process of assembling into a three-dimensional network structure, thereby affecting the orderliness and defects of the three-dimensional network structure, which not only improves the smoke suppression performance of the smoke suppressant, but also the asphalt smoke suppressants prepared from different types of acidic substances have different properties and can achieve different smoke suppression performances. Therefore, the smoke suppressant prepared by the preparation method can be suitable for different types of asphalt, broadens the application scenarios of metal organic framework-based asphalt smoke suppressants, and improves the universality of metal organic framework-based asphalt smoke suppressants.

[0058] The preparation method of this embodiment uses terephthalic acid, zirconium oxychloride octahydrate and an acidic modulator as raw materials to synthesize a metal organic framework-based asphalt smoke suppressant, which has a simple process and low cost. The zirconium oxychloride octahydrate is hydrolyzed and polymerized to form zirconium oxygen clusters, and the carboxyl group of terephthalic acid is deprotonated to form terephthalate radicals. The terephthalate radicals are coordinated with the zirconium oxygen clusters to form zirconium-carboxylic acid coordination bonds, and the zirconium oxygen clusters are used as nodes and the terephthalate radicals are used as bridging ligands to assemble into a three-dimensional network structure, which has good compatibility with petroleum asphalt and avoids serious segregation. At the same time, the three-dimensional network structure is an ultra-porous structure with a high specific surface area, which can effectively suppress the harmful exhaust gas generated by heating asphalt. Due to the "maze effect" caused by the porous structure, the harmful smoke of asphalt can be sealed and confined for a long time, which has a good odor-removing and smoke-suppressing effect, and has a good effect on VOCs and H 2 S, CO, SO 2 It can achieve efficient suppression of NO and has good universality in smoke suppression, which is beneficial to the low-carbon, environmentally friendly and low-harm of asphalt pavement, and has good economic and environmental benefits.

[0059] Embodiment 2

[0060] On the basis of Example 1, this example provides an asphalt smoke suppressant for roads. The asphalt smoke suppressant is prepared by the preparation method of Example 1. The asphalt smoke suppressant is a metal organic framework-based asphalt smoke suppressant with a three-dimensional network structure.

[0061] Specifically, the crystal form of the asphalt smoke suppressant can be a spherical crystal form or a regular octahedral crystal form; when the crystal form is a spherical crystal form, the particle size is 50nm-150nm, and the specific surface area is 600m 2 / g-900m 2 / g; when the crystal form is regular octahedral, the particle size is 200nm-500nm, and the specific surface area is 900m 2 / g-1300m 2 / g.

[0062] The metal organic framework-based asphalt smoke suppressant of this embodiment can reduce the problem of uncontrollable smoke emissions during the heating process of asphalt materials, reduce the generation of harmful smoke during asphalt heating and asphalt mixture mixing and paving, reduce smoke pollution to the environment, and reduce the health damage caused to road construction workers by smoke exposure.

[0063] Embodiment 3

[0064] Based on the first and second embodiments, this embodiment provides a road smoke suppression asphalt and a preparation method thereof. The road smoke suppression asphalt preparation method comprises the following steps:

[0065] Take 1 part of asphalt at 120°C-150°C, add 0.005-0.015 parts of the metal organic framework-based asphalt smoke suppressant of Example 2 and stir to obtain a low-odor smoke suppressant asphalt.

[0066] Specifically, the asphalt includes one or more of base asphalt and modified asphalt. The stirring speed is 500 rpm-2500 rpm, and the stirring time is 20 min-60 min.

[0067] It can be understood that the smoke suppressant asphalt for roads prepared by the above preparation method includes 1 part of asphalt and 0.005-0.015 parts of metal organic framework-based asphalt smoke suppressant.

[0068] Embodiment 4

[0069] Based on the first, second and third embodiments, this embodiment illustrates the asphalt smoke suppressant for roads and the smoke suppressant asphalt through the following examples.

[0070] Example 1

[0071] The preparation method of the asphalt smoke suppressant for roads provided in this example comprises the following steps:

[0072] S1. Blend zirconium oxychloride octahydrate and terephthalic acid in a mass ratio of 1:1 at 25° C. and grind them thoroughly in a mortar for 15 minutes to obtain a solid-solid blend.

[0073] S2. Add N,N-dimethylformamide to the solid-solid blend, wherein the mass ratio of the solid-solid blend to N,N-dimethylformamide is 1:100, and stir the mixture thoroughly using a constant temperature magnetic stirrer at 60° C. to obtain a mixed solution.

[0074] S3. Transfer the mixed solution into a hydrothermal reactor, add a mixed solution of formic acid and acetic acid as an acidic modulator, the mass ratio of formic acid to acetic acid is 1:4, the mass ratio of the mixed solution to the acidic modulator is 4:1, and react at 120°C for 20h.

[0075] S4. After the reaction is completed, the reaction solid product is taken out after standing for 10 hours, and the reaction solid product is washed with ethanol and deionized water alternately for 4 times; then the reaction solid product is dried in a vacuum drying oven at 80°C for 24 hours to obtain a metal organic framework-based asphalt smoke suppressant.

[0076] Furthermore, 100 parts of 90# asphalt were heated to 140°C, 1 part of the above-mentioned asphalt smoke suppressant was added thereto, and the mixture was stirred at a high speed of 1000 rpm for 1 hour to obtain a low-odor modified smoke suppressant asphalt.

[0077] Example 2

[0078] The preparation method of the asphalt smoke suppressant for roads provided in this example comprises the following steps:

[0079] S1. Blend zirconium oxychloride octahydrate and terephthalic acid in a mass ratio of 1:1.5 at 25°C, and grind them thoroughly in a mortar for 15 minutes to obtain a solid-solid blend.

[0080] S2. Add N,N-dimethylformamide to the solid-solid blend, wherein the mass ratio of the solid-solid blend to N,N-dimethylformamide is 1:100, and stir the mixture thoroughly using a constant temperature magnetic stirrer at 60° C. to obtain a mixed solution.

[0081] S3. Transfer the mixed solution into a hydrothermal reactor, add a mixed solution of formic acid and acetic acid as an acidic modulator, the mass ratio of formic acid to acetic acid is 1:4, the mass ratio of the mixed solution to the acidic modulator is 4:1, and react at 120°C for 30h.

[0082] S4. After the reaction is completed, the reaction solid product is taken out after standing for 10 hours, and the reaction solid product is washed with ethanol and deionized water alternately for 4 times; then the reaction solid product is dried in a vacuum drying oven at 80°C for 24 hours to obtain a metal organic framework-based asphalt smoke suppressant.

[0083] Furthermore, 100 parts of 90# asphalt were heated to 140°C, 1 part of the above-mentioned asphalt smoke suppressant was added thereto, and the mixture was stirred at a high speed of 1000 rpm for 1 hour to obtain a low-odor modified smoke suppressant asphalt.

[0084] Example 3

[0085] The method for preparing the asphalt smoke suppressant for roads provided in this example comprises the following steps:

[0086] S1. Blend zirconium oxychloride octahydrate and terephthalic acid in a mass ratio of 1:1 at 25°C, and grind them thoroughly in a mortar for 15 minutes to obtain a solid-solid blend.

[0087] S2. Add N,N-dimethylformamide to the solid-solid blend, wherein the mass ratio of the solid-solid blend to N,N-dimethylformamide is 1:100, and stir the mixture thoroughly using a constant temperature magnetic stirrer at 60° C. to obtain a mixed solution.

[0088] S3. Transfer the mixed solution into a hydrothermal reactor, add a mixed solution of formic acid and acetic acid as an acidic modulator, the mass ratio of formic acid to acetic acid is 1:4, the mass ratio of the mixed solution to the acidic modulator is 5:1, and react at 120°C for 20h.

[0089] S4. After the reaction is completed, the reaction solid product is taken out after standing for 10 hours, and the reaction solid product is washed with ethanol and deionized water alternately for 4 times; then the reaction solid product is dried in a vacuum drying oven at 80°C for 24 hours to obtain a metal organic framework-based asphalt smoke suppressant.

[0090] Furthermore, 100 parts of 90# asphalt were heated to 140°C, 1 part of the above-mentioned asphalt smoke suppressant was added thereto, and the mixture was stirred at a high speed of 1000 rpm for 1 hour to obtain a low-odor modified smoke suppressant asphalt.

[0091] Example 4

[0092] The preparation method of the asphalt smoke suppressant for roads provided in this example comprises the following steps:

[0093] S1. Blend zirconium oxychloride octahydrate and terephthalic acid in a mass ratio of 1:1 at 25°C, and grind them thoroughly in a mortar for 15 minutes to obtain a solid-solid blend.

[0094] S2. Add N,N-dimethylformamide to the solid-solid blend, wherein the mass ratio of the solid-solid blend to N,N-dimethylformamide is 1:100, and stir the mixture thoroughly using a constant temperature magnetic stirrer at 60° C. to obtain a mixed solution.

[0095] S3. Transfer the mixed solution into a hydrothermal reactor, add acetic acid as an acidic modulator, the mass ratio of the mixed solution to acetic acid is 4:1, and react at 120° C. for 20 h.

[0096] S4. After the reaction is completed, the reaction solid product is taken out after standing for 10 hours, and the reaction solid product is washed with ethanol and deionized water alternately for 4 times; then the reaction solid product is dried in a vacuum drying oven at 80°C for 24 hours to obtain a metal organic framework-based asphalt smoke suppressant.

[0097] Furthermore, 100 parts of 90# asphalt were heated to 140°C, 1 part of the above-mentioned asphalt smoke suppressant was added thereto, and the mixture was stirred at a high speed of 1000 rpm for 1 hour to obtain a low-odor modified smoke suppressant asphalt.

[0098] Example 5

[0099] The preparation method of the asphalt smoke suppressant for roads provided in this example comprises the following steps:

[0100] S1. Blend zirconium oxychloride octahydrate and terephthalic acid in a mass ratio of 1:1 at 25°C, and grind them thoroughly in a mortar for 15 minutes to obtain a solid-solid blend.

[0101] S2. Add N,N-dimethylformamide to the solid-solid blend, wherein the mass ratio of the solid-solid blend to N,N-dimethylformamide is 1:100, and stir the mixture thoroughly using a constant temperature magnetic stirrer at 60° C. to obtain a mixed solution.

[0102] S3. Transfer the mixed solution into a hydrothermal reactor, add concentrated hydrochloric acid as an acidic modulator, the mass ratio of the mixed solution to the concentrated hydrochloric acid is 4:1, and react at 120°C for 20h.

[0103] S4. After the reaction is completed, the reaction solid product is taken out after standing for 10 hours, and the reaction solid product is washed with ethanol and deionized water alternately for 4 times; then the reaction solid product is dried in a vacuum drying oven at 80°C for 24 hours to obtain a metal organic framework-based asphalt smoke suppressant.

[0104] Furthermore, 100 parts of 90# asphalt were heated to 140°C, 1 part of the above-mentioned asphalt smoke suppressant was added thereto, and the mixture was stirred at a high speed of 1000 rpm for 1 hour to obtain a low-odor modified smoke suppressant asphalt.

[0105] Comparative Example

[0106] In this example, no modifier is added to prepare the road asphalt smoke suppressant, and the preparation method includes the steps of:

[0107] S1. Blend zirconium oxychloride octahydrate and terephthalic acid in a mass ratio of 1:1 at 25°C, and grind them thoroughly in a mortar for 15 minutes to obtain a solid-solid blend.

[0108] S2. Add N,N-dimethylformamide to the solid-solid blend, wherein the mass ratio of the solid-solid blend to N,N-dimethylformamide is 1:100, and stir the mixture thoroughly using a constant temperature magnetic stirrer at 60° C. to obtain a mixed solution.

[0109] S3. Transfer the mixed solution into a hydrothermal reactor, without adding a modulator, and react at 120° C. for 20 h.

[0110] S4. After the reaction is completed, the reaction solid product is taken out after standing for 10 hours, and the reaction solid product is washed with ethanol and deionized water alternately for 4 times; then the reaction solid product is dried in a vacuum drying oven at 80°C for 24 hours to obtain a metal organic framework-based asphalt smoke suppressant.

[0111] Furthermore, 100 parts of 90# asphalt were heated to 140°C, 1 part of the above-mentioned asphalt smoke suppressant was added thereto, and the mixture was stirred at a high speed of 1000 rpm for 1 hour to obtain a low-odor modified smoke suppressant asphalt.

[0112] In this embodiment, the microscopic morphology and specific surface area of ​​the asphalt smoke suppressants of Examples 1-5 and the comparative example were observed. Figure 2a-2f As shown, Figure 2a-2e The microscopic morphology of the asphalt smoke suppressant provided in this embodiment is as follows: Figure 2a , Figure 2b , Figure 2c , Figure 2d , Figure 2e The microscopic morphology of asphalt smoke suppressants of Example 1, Example 2, Example 3, Example 4, and Example 5 are shown in order. Figure 2f This is the microscopic morphology of the asphalt smoke suppressant of the comparative example.

[0113] It can be seen from the microscopic morphology that the asphalt smoke suppressant crystals in the comparative example are tetrahedral, with a specific surface area of ​​864.4m² / g. The asphalt smoke suppressants in Examples 1 to 5 are affected by the modulator, and the particles are relatively dispersed. The asphalt smoke suppressant crystals in Example 1 are octahedral, with a specific surface area of ​​1164.4m² / g. In Example 2, after increasing the amount of terephthalic acid, the particle size of the smoke suppressant increased, and the crystals were octahedral, with a specific surface area of ​​1001.4m² / g. In Example 3, after reducing the blending ratio of the mixed solution and the acidic modulator, the octahedral crystal form of the smoke suppressant became more obvious, and the particle size was more uniform, with a particle size of 200nm and a specific surface area of ​​1278m 2 Example 4: When acetic acid is used alone as an acidic modulator, two types of octahedral crystal smoke suppressants with particle sizes of 200 nm and 500 nm are formed, and the specific surface area ranges from 800 m 2 / g-1000m 2 / g; In Examples 1, 2, and 3, when formic acid and acetic acid are mixed as acidic modulators, only 200nm octahedral crystals are formed, and the specific surface area ranges from 900m 2 / g-1300m 2 Example 5 When concentrated hydrochloric acid is used as the acidic modulator, the smoke suppressant formed has a rich pore structure, the crystals are spherical, the product particle size is uniform, the particle size is 100nm, and the specific surface area is 758m 2 / g.

[0114] This example uses the Wanandi GAS Tiger 6000-6X-NA gas detector equipped with TVOCs sensors, SO 2 Sensor, NO X Sensor, H 2 The S sensor and CO sensor tested the concentration of harmful gases at 140°C on the smoke suppression asphalt of Examples 1-5, the smoke suppression asphalt of the comparative example, and 90# asphalt, wherein the smoke suppression asphalt of the comparative example and 90# asphalt were used as the control group, and the penetration, softening point and ductility of the above asphalt were tested. The test results are shown in Table 1.

[0115] Table 1 Asphalt technical indicators

[0116]

[0117] As shown in Table 1, after adding smoke suppressant to 90# asphalt, the penetration, softening point and ductility of asphalt are basically unchanged; the inhibition rate of TVOCs in the comparative example is 45.5%, and the inhibition rates of TVOCs in Examples 1 to 5 are 68.8%, 53.3%, 51.5%, 50.1% and 50.5%, respectively. The product obtained by using the mixture of formic acid and acetic acid as the acidic modulator has excellent VOCs inhibition effect; the inhibition rate of H 2 The inhibition rate of S was 28.5%, and the inhibition rate of Examples 1-5 on H 2 The inhibition rates of S were 76.7%, 46%, 36%, 29% and 59%, and the smoke suppressant obtained by using the mixture of formic acid and acetic acid as the acid modulator had a significant effect on H 2 S has a good inhibitory effect; the inhibition rate of the comparative example on CO is 28%, and the inhibition rates of Examples 1 to 5 on CO are 65%, 39%, 33%, 22%, and 41%, respectively. The smoke suppressant obtained by using a mixture of formic acid and acetic acid as an acidic modulator has a good inhibitory effect on CO; the comparative example has a good inhibitory effect on SO 2 The inhibition rate of Example 1-Example 5 was 41%. 2 The inhibition rates were 81%, 50%, 41%, 50% and 83% respectively. The inhibitors obtained by using the mixture of formic acid and acetic acid as the acid modulator and the inorganic acid as the acid modulator had a significant effect on SO 2 All of them have good inhibitory effect; the comparative example has good inhibitory effect on NO X The inhibition rate of Example 1-Example 5 was 63%. X The inhibition rates were 90%, 72%, 82%, 76% and 85% respectively. The smoke suppressant obtained by using the mixture of formic acid and acetic acid as the acid modulator had a significant effect on NO X In summary, Example 1 has the best inhibitory effect on asphalt fume, and Example 5 has an excellent inhibitory effect on inorganic harmful fume, and the fume inhibition effect of Example 1 is better than that of Example 5.

[0118] In summary, in this embodiment, zirconium oxychloride octahydrate and terephthalic acid are used as the main ligands to synthesize a metal organic framework-based asphalt smoke suppressant, and the metal organic framework-based asphalt smoke suppressant is mixed with base asphalt or modified asphalt at high temperature to achieve the purpose of suppressing volatile organic compounds TVOCs and SO 2 , H 2 S, CO, NO x Comprehensive suppression is carried out to effectively reduce the smoke of base asphalt and modified asphalt.

[0119] The above contents are further detailed descriptions of the present invention in combination with specific preferred embodiments, and it cannot be determined that the specific implementation of the present invention is limited to these descriptions. For ordinary technicians in the technical field to which the present invention belongs, several simple deductions or substitutions can be made without departing from the concept of the present invention, which should be regarded as falling within the protection scope of the present invention.

Claims

1. A method for preparing an asphalt smoke suppressant for roads, characterized in that: Includes steps: S1. Blending zirconium oxychloride octahydrate with terephthalic acid at 5°C-40°C, and grinding for 15min-30min to obtain a solid-solid blend; the mass ratio of the zirconium oxychloride octahydrate to the terephthalic acid is 1:(1-2); S2, adding N,N-dimethylformamide to the solid-solid blend and stirring at a constant temperature to dissolve the solid-solid blend to obtain a mixed solution; the mass ratio of the solid-solid blend to the N,N-dimethylformamide is 1:(100-200); S3, transferring the mixed solution into a high pressure reactor or a hydrothermal reactor, and adding an acidic modulator to form a reaction system, allowing the reaction system to react at 80°C-140°C for 10h-30h; the acidic modulator includes formic acid and acetic acid, and the mass ratio of formic acid to acetic acid is 1:4; the mass ratio of the acidic modulator to the mixed solution is 1:(4-5); S4. After the reaction is completed, the reaction solid product is allowed to stand for a period of time to obtain the reaction solid product, and the reaction solid product is cleaned and dried to obtain a metal organic framework-based asphalt smoke suppressant with a three-dimensional network structure; the metal organic framework-based asphalt smoke suppressant is used to suppress volatile substances TVOCs, SO2, H2S, CO and NO in road asphalt x .

2. The method for preparing the road asphalt smoke suppressant according to claim 1, characterized in that: Step S2 includes: The N,N-dimethylformamide is added to the solid-solid blend, and the mixture is stirred at a constant temperature of 45° C. to 85° C. for 1 h to 3 h to dissolve the solid-solid blend, thereby obtaining the mixed solution.

3. The method for preparing the road asphalt smoke suppressant according to claim 1, characterized in that: Step S4 includes: After the reaction is completed, the solid product is allowed to stand for 8 hours to 24 hours, and the solid product is taken out and washed alternately with ethanol and deionized water for 2 to 4 times; The cleaned reaction solid product is dried in a vacuum drying oven at 70° C. to 110° C. for 10 h to 24 h to obtain the metal organic framework-based asphalt smoke suppressant.

4. A road asphalt smoke suppressant, characterized in that: The asphalt smoke suppressant is prepared by the preparation method according to any one of claims 1 to 3, and the asphalt smoke suppressant is a metal organic framework-based asphalt smoke suppressant with a three-dimensional network structure.

5. A method for preparing smoke-suppressing asphalt for roads, characterized in that: Includes steps: Take 1 part of asphalt at 120°C-150°C, add 0.005-0.015 parts of the road asphalt smoke suppressant as claimed in claim 4 and stir to obtain smoke suppressant asphalt.

6. A smoke-suppressing asphalt for roads, characterized in that: The preparation method as claimed in claim 5 comprises: 1 part of asphalt and 0.005-0.015 parts of metal organic framework based asphalt smoke suppressant.

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