MOFs-based rubber asphalt VOCs inhibitor, smoke-suppressing rubber asphalt and preparation method

Abstract

The invention discloses a rubber asphalt VOCs inhibitor based on MOFs material, a smoke-suppressing rubber asphalt and a preparation method thereof. The chemical formula of the inhibitor is C x H y O 32 Zr 6 , where x=48-120, y=28-76, it is a zirconium-based metal organic framework material with a cubic crystal structure, a crystal pore size of 0.5-2nm, and a specific surface area of ​​1000-3200m 2 / g, the inhibitor can significantly reduce the types and amounts of VOCs released from rubber asphalt. The smoke-suppressing rubber asphalt prepared with the inhibitor can reduce the types of VOCs released from 87 to 20, and the concentrations of aliphatic hydrocarbons, aromatic hydrocarbons, and hydrocarbon derivatives can be reduced by 60-82%, and the concentration of sulfur-containing compounds can be reduced by 90%; in particular, the inhibitory effect on a class of carcinogens is particularly significant, with an inhibition rate of up to 92.4%, which can reduce the harm to human health during the construction of rubber asphalt, and has broad market application prospects.

Description

Technical Field

[0001] The present invention belongs to the technical field of inhibition of volatile organic compounds in rubber asphalt, and more specifically, relates to a rubber asphalt VOCs inhibitor based on MOFs materials, a smoke-suppressing rubber asphalt and a preparation method thereof. Background Art

[0002] With the rapid development of the automobile industry, about 1.5 billion tires are produced worldwide each year, and the number continues to grow at a high rate, posing a severe challenge to the environment. The number of discarded rubber products continues to increase, gradually becoming the world's largest solid waste residue, and its disposal has gradually become a burden on social environmental governance. The technology of further preparing rubber powder into rubber asphalt has significant economic benefits. It is an internationally recognized method for resource utilization and harmless treatment of waste tires, and is also a key means to improve the performance of traditional petroleum asphalt.

[0003] However, compared with ordinary base asphalt, rubber asphalt has a higher viscosity, higher preparation and construction temperature, and releases more types and larger quantities of volatile organic compounds (Volatile Organic Compounds, VOCs). Rubber asphalt will produce more than 100 kinds of volatile organic compounds during the preparation and on-site construction process. These volatile organic compounds have low boiling points and are easy to volatilize, causing serious harm to human health and the environment. It also contains a class of carcinogens such as 1,3-butadiene, benzene, trichloroethylene and 1,2-dichloropropane, which are volatile organic substances that need to be suppressed. In view of the huge potential harm of asphalt VOCs to the human body and the environment, researchers at home and abroad have done some research work on VOCs inhibition, which is of great significance for reducing the release of asphalt VOCs.

[0004] However, currently, VOCs inhibitors mainly use inorganic porous materials, which have low selectivity and low efficiency in inhibiting VOCs, which is not conducive to the promotion of practical engineering applications. Among them, patent CN 114773635 A discloses a low-VOCs rubber granule, rubber asphalt and its preparation method, which uses water-based polyurethane, water-based epoxy resin or SBS emulsion to wrap the surface of rubber powder to prepare low-VOCs rubber granules and rubber asphalt. However, the rubber granules prepared by this method have a small specific surface area and poor reaction activity, and the VOCs inhibition effect on rubber asphalt is not obvious at this stage.

[0005] In addition, patent CN 110294864 A "A VOCs inhibitor for asphalt based on FCC waste catalyst, smoke suppression asphalt and its preparation method" uses the porous molecular sieve structure on the surface of FCC (Fluid Catalytic Cracking) waste catalyst to adsorb small molecules in asphalt, but FCC waste catalyst contains heavy metal ions, which will pollute the soil, groundwater and atmosphere. Therefore, the study of a green, environmentally friendly and efficient VOCs inhibitor for rubber asphalt is conducive to reducing the release of VOCs in asphalt, which is of great significance to human health and environmental protection. Summary of the invention

[0006] In view of the above defects or improvement needs of the prior art, the present invention provides a rubber asphalt VOCs inhibitor, a smoke-suppressing rubber asphalt and a preparation method based on MOFs materials, the purpose of which is to use any one of terephthalic acid, 4,4'-biphenyl dicarboxylic acid, 1,1':3',1"-terphenyl-4,4"-dicarboxylic acid as an organic ligand, and add zirconium chloride to the organic ligand in a molar ratio of 1:1 to 6 to prepare a cubic crystal structure of zirconium-based metal organic framework material, the chemical formula of which is C x H y O 32 Zr6, x = 48 ~ 120, y = 28 ~ 76, crystal pore size is 0.5 ~ 2nm, specific surface area is 1000 ~ 3200m 2 / g, and found that the material with this pore size can well adsorb VOCs in rubber asphalt and reduce the concentration of VOCs, especially for 1,3-butadiene, benzene, trichloroethylene and 1,2-dichloropropane, and can significantly inhibit the release of a class of carcinogens, thereby solving the technical problem that the existing VOCs inhibitors have poor inhibitory effect on the release of VOCs in rubber asphalt.

[0007] To achieve the above object, according to one aspect of the present invention, a rubber asphalt VOCs inhibitor based on MOFs material is provided, wherein the rubber asphalt VOCs inhibitor has a chemical formula of C x H y O 32 Zr6, x = 48 ~ 120, y = 28 ~ 76, is a zirconium-based metal organic framework material with a cubic crystal structure, a crystal pore size of 0.5 ~ 2nm, and a specific surface area of ​​1000 ~ 3200m 2 / g.

[0008] Preferably, the rubber asphalt VOCs inhibitor based on MOFs material has a crystal morphology size of 100nm to 3.0μm, a crystal pore size of 1 to 2nm, and a specific surface area of ​​2000 to 3200m 2 / g.

[0009] According to another aspect of the present invention, there is also provided a method for preparing the rubber asphalt VOCs inhibitor based on the MOFs material as described in the present invention, which comprises the following steps:

[0010] Add zirconium chloride to N,N-dimethylformamide and stir at a constant temperature, add an organic ligand and acetic acid respectively, and stir at a constant temperature to obtain a mixed solution;

[0011] The obtained mixed solution is reacted at 100-160° C. for 12-24 hours, and naturally cooled to room temperature after the reaction is completed; and washed with N, N-dimethylformamide and methanol, and centrifuged multiple times to obtain a precipitate, which is the MOFs-based rubber asphalt VOCs inhibitor after drying;

[0012] The zirconium chloride, N,N-dimethylformamide, organic ligand and acetic acid are added in a molar ratio of 1:400-600:1-6:5-105 respectively;

[0013] The organic ligand includes one or more combinations of terephthalic acid, 4,4'-biphenyldicarboxylic acid, and 1,1':3',1"-terphenyl-4,4"-dicarboxylic acid.

[0014] Preferably, in the preparation method of the rubber asphalt VOCs inhibitor based on MOFs material, the content of C8H6O4 of terephthalic acid is ≥98.0wt%, the content of C8H6O4 of 4,4'-biphenyl dicarboxylic acid is ≥98.0wt%. 14 H 10 O4 content ≥ 97.0wt%, 1,1':3',1"-terphenyl-4,4"-dicarboxylic acid C 20 H 14 The content of O4 is ≥98.0wt%; the content of CH3COOH in the acetic acid is ≥99.5wt%.

[0015] Preferably, in the method for preparing the rubber asphalt VOCs inhibitor based on MOFs material, the acetic acid is added at a flow rate of 1 to 10 mL / min.

[0016] Preferably, in the preparation method of the rubber asphalt VOCs inhibitor based on MOFs material, when the zirconium chloride is added to N,N-dimethylformamide, it is stirred at a constant temperature of 30-80°C for 15-30 minutes; when the organic ligand is added, it is stirred at a constant temperature of 20-60°C for 15-30 minutes; when acetic acid is added, it is stirred at a constant temperature of 40-60°C for 30-60 minutes.

[0017] According to another aspect of the present invention, there is also provided an application of the rubber asphalt VOCs inhibitor based on the MOFs material as described in the present invention, which is used for adsorbing volatile organic compounds in rubber asphalt.

[0018] Preferably, the application of the rubber asphalt VOCs inhibitor based on MOFs material is used to adsorb 1,3-butadiene, benzene, trichloroethylene and 1,2-dichloropropane in the volatile organic compounds of rubber asphalt.

[0019] According to another aspect of the present invention, a smoke-suppressing rubber asphalt is provided, which comprises, by weight, 70-90 parts of asphalt, 10-30 parts of rubber powder and 0.1-1 part of the rubber asphalt VOCs inhibitor based on the MOFs material as described in the present invention.

[0020] Preferably, the smoke-suppressing rubber asphalt is obtained according to the following preparation method:

[0021] Take 70-90 parts of base asphalt at 160°C to 170°C and 10-30 parts of rubber powder, mix and shear at a shear speed of 4000-8000 r / min and a shear time of 40-60 min to obtain rubber asphalt;

[0022] 0.1 to 1 part of the rubber asphalt VOCs inhibitor of the present invention is added to the rubber asphalt for shearing, the shear rate is 4000 to 8000 r / min, the shearing time is 20 to 40 min, and the temperature is kept at 160° C. to 170° C. during the shearing process; after the shearing is completed, the smoke-suppressing rubber asphalt is obtained.

[0023] In general, the above technical solution conceived by the present invention can achieve the following beneficial effects compared with the prior art due to the rubber asphalt VOCs inhibitor provided by the present invention:

[0024] The rubber asphalt VOCs inhibitor provided by the present invention is an organic zirconium-based metal organic framework material, which has a cubic crystal structure and a pore size of 0.5 to 2 nm. VOCs molecules collide and squeeze into the internal pores of MOFs molecules, which can effectively adsorb rubber asphalt VOCs molecules. At the same time, the small pore size can prevent asphalt from entering the interior and clogging the material. In addition, the unsaturated metal Zr in the MOFs material 3+ Unstable and active, when in contact with VOCs molecules, Zr 3+ The electron cloud density at the metal site shifts, and part of the charge is transferred to the VOCs molecules to form chemical bonds, which can enhance the adsorption effect and has high selectivity. It can significantly reduce the types and amounts of VOCs released from rubber asphalt, reduce the environmental pollution caused by the construction of rubber asphalt, and promote the promotion and application of rubber asphalt.

[0025] And the specific surface area is 1000~3200m 2 / g, and its large specific surface area makes it compatible with asphalt. The ΔS value of the MOFs material and asphalt separation test results is 0.4-0.8, which is far below the specification requirements. Asphalt is a complex organic mixture composed of saturated components, aromatic components, colloids and asphaltene, while the ligands of the MOFs material are organic structures, such as terephthalic acid, 4,4'-biphenyl dicarboxylic acid, 1,1':3' or 1"-terphenyl-4,4"-dicarboxylic acid. According to the principle of similar compatibility, the compatibility of the MOFs material with asphalt is better than that of inorganic materials.

[0026] In addition, the smoke-suppressing rubber asphalt provided by the present invention, due to the addition of the rubber asphalt VOCs inhibitor provided by the present invention, the types of VOCs released can be reduced from 87 to 20, and the concentrations of aliphatic hydrocarbons, aromatic hydrocarbons, and hydrocarbon derivatives can be reduced by 60-82%, and the concentration of sulfur-containing compounds can be reduced by 90%; in particular, the inhibitory effect on a class of carcinogens is particularly significant, with an inhibition rate of up to 92.4%, which can reduce the harm to human health during the construction process of rubber asphalt, and has broad market application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 This is the microscopic surface morphology of the rubber asphalt VOCs inhibitor based on MOFs material;

[0028] Figure 1 a in the figure is the microscopic surface morphology of the rubber asphalt VOCs inhibitor in Example 1; Figure 1 b is the microscopic surface morphology of the rubber asphalt VOCs inhibitor in Example 2; Figure 1 c is the microscopic surface morphology of the rubber asphalt VOCs inhibitor in Example 3;

[0029] Figure 2 This is a comparison chart of the inhibitory effects of the smoke-suppressing rubber asphalt of the present invention and common rubber asphalt on the release of a type of carcinogen;

[0030] Figure 3 This is a comparison chart of the types of VOCs released by the smoke-suppressing rubber asphalt in the present invention and ordinary rubber asphalt. DETAILED DESCRIPTION

[0031] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0032] Metal organic frameworks (MOFs) are a type of coordination polymer with a three-dimensional pore structure. They generally use metal ions as connection points and organic ligands as support to form a 3D extension in space. By introducing different metal ions and organic ligands to participate in the assembly of coordination polymers, MOFs materials with different pore sizes and specific surface areas can be obtained.

[0033] At present, the most studied MOFs materials are zirconium-based metal organic framework materials, which are mainly used in photocatalysts, gas storage, detection of trivalent iron ions in water, and gas adsorption and separation. For example, the zirconium-based metal organic framework materials in patent CN113087918A are used to adsorb and separate carbon dioxide, propylene and ethylene gases in the atmosphere, but they have large pores and small specific surface areas (pore size is 0.06-5μm, specific surface area is 600-1300m 2 / g) has a poor adsorption effect on volatile substances, and there is little research on the inhibition of organic volatiles in rubber asphalt by MOFs, and its inhibitory effect on VOCs in rubber asphalt is still unclear.

[0034] This study found that any one of terephthalic acid, 4,4'-biphenyl dicarboxylic acid, and 1,1':3',1"-terphenyl-4,4"-dicarboxylic acid was used as an organic ligand, wherein zirconium chloride and the organic ligand were added in a molar ratio of 1:1 to 6, and a zirconium-based metal organic framework material with a chemical formula of C x H y O 32 Zr6; x = 48 ~ 120; y = 28 ~ 76, the organic material has a cubic crystal structure, a pore size of 0.5 ~ 2nm, and a specific surface area of ​​1000 ~ 3200m 2 / g. The material has a large specific surface area and good compatibility with rubber asphalt, and its small pore size can prevent asphalt from entering the material and blocking the pores, which is conducive to the targeted adsorption of volatile substances. It can significantly reduce the number of VOCs in rubber asphalt (VOCs concentration is reduced by 89.4%), especially significantly reduce the concentration of aliphatic hydrocarbons, aromatic hydrocarbons, hydrocarbon derivatives and sulfur-containing compounds, especially for a class of carcinogens such as 1,3-butadiene, benzene, trichloroethylene and 1,2-dichloropropane. The inhibition rate is as high as 84%-92.4%.

[0035] The present invention provides a rubber asphalt VOCs inhibitor based on MOFs material, which is a zirconium-based metal organic framework material, and the chemical formula of the zirconium-based metal organic framework material is C x H y O 32 Zr6, x = 48 ~ 120, y = 28 ~ 76, its crystal pore size is 0.5 ~ 2nm, and the specific surface area is 1000 ~ 3200m 2 / g;

[0036] The preferred crystal morphology is small cubic crystals with a diameter of 100nm to 3.0μm, a pore size of 1 to 2nm, and a specific surface area of ​​2000 to 3200m 2 / g of zirconium-based metal-organic framework materials.

[0037] The present invention also provides a method for preparing a rubber asphalt VOCs inhibitor based on MOFs material, comprising the following steps:

[0038] (1) adding zirconium chloride to N,N-dimethylformamide and stirring at a constant temperature to obtain solution A; stirring at a constant temperature of 60° C. for 15 to 30 minutes; the zirconium chloride and N,N-dimethylformamide are added in a molar ratio of 1:400 to 600;

[0039] (2) adding a preset ratio of organic ligands to the obtained solution A, and stirring at a constant temperature to obtain solution B, such as stirring at a constant temperature of 60° C. for 15 to 30 minutes, to obtain solution B; the preset ratio is a molar ratio of zirconium chloride: organic ligand of 1:1 to 6; the organic ligand includes one or more combinations of terephthalic acid, 4,4'-biphenyldicarboxylic acid, and 1,1':3',1"-terphenyl-4,4"-dicarboxylic acid;

[0040] The experiment found that the MOFs material prepared by using any one of terephthalic acid, 4,4'-biphenyl dicarboxylic acid, 1,1':3',1"-terphenyl-4,4"-dicarboxylic acid as the organic ligand and the molar ratio of zirconium chloride: organic ligand is 1:1-6 has large pore size and specific surface area, among which the pore size is 0.5-2nm and the specific surface area is 1000-3200m 2 / g, it has strong adsorption capacity for VOCs in rubber asphalt, especially for 1,3-butadiene, benzene, trichloroethylene and 1,2-dichloropropane. It can significantly inhibit the release of these carcinogens in rubber asphalt and reduce the damage to the human body.

[0041] Preferably, the content of C8H6O4 in terephthalic acid is ≥98.0wt%, the content of C8H6O4 in 4,4'-biphenyldicarboxylic acid is ≥98.0wt%. 14 H 10 O4 content ≥ 97.0wt%, 1,1':3',1"-terphenyl-4,4"-dicarboxylic acid C 20 H 14 The content of O4 is ≥98.0wt%; the content of ZrCl4 in the zirconium chloride is ≥99.8wt%.

[0042] (3) adding a preset amount of acetic acid to the solution B at a flow rate of 1 to 10 mL / min, stirring at a constant temperature to obtain a solution C, such as stirring at a constant temperature of 60° C. for 30 to 60 min; the preset amount is calculated based on a molar ratio of zirconium chloride to acetic acid of 1:5 to 105;

[0043] Preferably, the CH3COOH content of the acetic acid is ≥99.5wt%.

[0044] (4) The obtained solution C is transferred to a reactor and reacted in an environment of 100 to 160° C. for 12 to 24 hours; after the reaction is completed, it is naturally cooled to room temperature to obtain a solution D; the obtained solution D is washed with N,N-dimethylformamide and methanol, respectively, and centrifuged multiple times to obtain a precipitate, which is dried to obtain the MOFs-based rubber asphalt VOCs inhibitor.

[0045] In some implementations, solution D is first washed with N,N-dimethylformamide, centrifuged at 6000-10000 rpm for 2-3 times, and then centrifuged at 6000-10000 rpm for 2-3 times with methanol to obtain a precipitate, which is dried at 60°C-80°C for 12-20 hours to obtain a zirconium-based metal organic framework material, i.e., the rubber asphalt VOCs inhibitor based on MOFs material.

[0046] In addition, the present invention also provides an application of a rubber asphalt VOCs inhibitor based on MOFs material, which is used to adsorb volatile organic compounds in rubber asphalt, especially 1,3-butadiene, benzene, trichloroethylene and 1,2-dichloropropane in the volatile organic compounds in rubber asphalt.

[0047] The present invention also provides a smoke-suppressing rubber asphalt, which comprises, by weight, 70-90 parts of asphalt, 10-30 parts of rubber powder and 0.1-1 part of the rubber asphalt VOCs inhibitor based on the MOFs material of the present invention.

[0048] The smoke-suppressing rubber asphalt is obtained according to the following preparation method:

[0049] The asphalt is heated to 160-170°C and stirred. During the stirring process, rubber powder is added in proportion. The shear speed is 4000-8000 r / min and the shear time is 40-60 min to obtain rubber asphalt.

[0050] 0.1 to 1 part of the rubber asphalt VOCs inhibitor of the present invention is added to the rubber asphalt for shearing, the shear rate is 4000-8000 r / min, the shearing time is 20-40 min, and the temperature is kept at 160° C.-170° C. during the shearing process; after the shearing is completed, smoke-suppressing rubber asphalt is obtained.

[0051] The following are examples:

[0052] Example 1 Rubber asphalt VOCs inhibitor based on MOFs material 1 (C 48 H 28 O 32 Zr6)

[0053] The rubber asphalt VOCs inhibitor 1 is UiO-66, the chemical formula is C 48 H 28 O 32 Zr6 is prepared specifically according to the following method:

[0054] 1) adding zirconium chloride to N,N-dimethylformamide at a molar ratio of zirconium chloride to N,N-dimethylformamide of 1:600, and stirring at 60° C. for 15 minutes to obtain solution A;

[0055] 2) adding an organic ligand in a molar ratio of zirconium chloride to terephthalic acid of 1:1, i.e., adding terephthalic acid to the solution A, and stirring at 60° C. for 15 minutes to obtain a solution B;

[0056] 3) adding acetic acid at a molar ratio of zirconium chloride to acetic acid of 1:5, wherein the acetic acid is uniformly added to the solution B at a flow rate of 2 mL / min, and stirred at 60° C. for 30 min to obtain a solution C;

[0057] 4) transferring the solution C to a reactor, sealing the reactor and placing it in an environment of 120° C. for reaction for 20 hours; cooling naturally to room temperature after the reaction to obtain a solution D;

[0058] 5) washing the solution D twice by centrifugation at 6000 rpm with N,N-dimethylformamide, and then washing it three times by centrifugation at 7000 rpm with methanol to obtain a precipitate; and then drying the precipitate at 60° C. for 16 h to obtain a zirconium-based metal organic framework material, i.e., the rubber asphalt VOCs inhibitor based on MOFs material.

[0059] Example 2 Rubber asphalt VOCs inhibitor based on MOFs material 2 (C 84 H 52 O 32 Zr6)

[0060] The rubber asphalt VOCs inhibitor is UiO-67, the chemical formula is C 84 H 52 O 32 Zr6 is prepared specifically according to the following method:

[0061] 1) adding zirconium chloride to N,N-dimethylformamide at a molar ratio of zirconium chloride to N,N-dimethylformamide of 1:500, and stirring at 60° C. for 30 min to obtain solution A;

[0062] 2) adding an organic ligand in a molar ratio of zirconium chloride to organic ligand 4,4'-biphenyldicarboxylic acid of 1:3, i.e., adding 4,4'-biphenyldicarboxylic acid to the solution A, stirring at 60° C. for 30 min, to obtain a solution B;

[0063] 3) adding acetic acid at a molar ratio of zirconium chloride to acetic acid of 1:50, wherein the acetic acid is uniformly added to the solution B at a flow rate of 8 mL / min, and stirred at 60° C. for 30 min to obtain a solution C;

[0064] 4) transferring the solution C to a reactor, sealing the reactor and placing it in an environment of 120° C. for reaction for 22 hours; after the reaction, naturally cooling it to room temperature to obtain a solution D;

[0065] 5) washing the solution D by centrifugation at 8000 rpm for 3 times with N,N-dimethylformamide, and then washing it by centrifugation at 8000 rpm for 3 times with methanol to obtain a precipitate; and then drying the precipitate at 80° C. for 18 h to obtain a zirconium-based metal organic framework material, which is the rubber asphalt VOCs inhibitor based on MOFs material.

[0066] Example 3 Rubber asphalt VOCs inhibitor based on MOFs material 3 (C 120 H 76 O 32 Zr6)

[0067] The rubber asphalt VOCs inhibitor is UiO-68, the chemical formula is C 120 H 76 O 32 Zr6 is prepared specifically according to the following method:

[0068] 1) adding zirconium chloride to N,N-dimethylformamide at a molar ratio of zirconium chloride to N,N-dimethylformamide of 1:400, and stirring at 60° C. for 25 minutes to obtain solution A;

[0069] 2) adding an organic ligand in a molar ratio of zirconium chloride to organic ligand 1,1':3',1"-terphenyl-4,4"-dicarboxylic acid of 1:5, i.e., adding the 1,1':3',1"-terphenyl-4,4"-dicarboxylic acid to the solution A, stirring at 60° C. for 25 min, to obtain a solution B;

[0070] 3) adding acetic acid at a molar ratio of zirconium chloride to acetic acid of 1:105, wherein the acetic acid is uniformly added to the solution B at a flow rate of 6 mL / min, and stirred at 60° C. for 20 min to obtain a solution C;

[0071] 4) transferring the solution C to a reactor, sealing the reactor and placing it in an environment of 120° C. for reaction for 24 hours; after the reaction, naturally cooling it to room temperature to obtain a solution D;

[0072] 5) washing the solution D by centrifugation at 8000 rpm for 3 times with N,N-dimethylformamide, and then washing it by centrifugation at 8000 rpm for 3 times with methanol to obtain a precipitate; and then drying the precipitate at 80° C. for 20 h to obtain a zirconium-based metal organic framework material, which is the rubber asphalt VOCs inhibitor based on MOFs material.

[0073] Determination of the microscopic morphology and specific surface area of ​​rubber asphalt VOCs inhibitors:

[0074] The rubber asphalt VOCs inhibitor obtained in Examples 1-3 was measured using an electron scanning microscope (SEM) and a fully automatic rapid specific surface area and porosity analyzer. The test results are as follows: Figure 1 As shown in Table 1, 1(a), 1(b), and 1(c) are scanning electron microscope images of the samples in Examples 1, 2, and 3, respectively.

[0075] Table 1

[0076] sample <![CDATA[Specific surface area (m 2 / g)]]> <![CDATA[Pore volume (cm 3 / g)]]> Pore ​​size (nm) Example 1 1337 0.48 1.92 Example 2 2108 1.03 1.71 Example 3 3149 1.34 1.62

[0077] Depend on Figure 1 (a) It can be seen that the crystal morphology of the sample in Example 1 is characterized by small cubic crystals of about 100 nm, which are stacked and agglomerated;

[0078] Depend on Figure 1 (b) It can be seen that the individual crystal morphology of the sample in Example 2 is relatively regular, and its crystal size is about 1.0 μm;

[0079] Depend on Figure 1 (c) It can be seen that the morphology of the sample in Example 3 becomes a regular cube, the crystals are relatively dispersed without agglomeration, and the crystal size is about 2.5 μm.

[0080] Example 4 Smoke Suppression Rubber Asphalt 1

[0081] The smoke-suppressing rubber asphalt comprises 79.4 parts of 70# base asphalt, 20 parts of rubber powder, and 0.6 parts of the rubber asphalt VOCs inhibitor of the MOFs material obtained in Example 1, and is specifically prepared according to the following method:

[0082] 79.4 parts of base asphalt were heated to 160°C and kept warm with stirring. During the stirring process, 20 parts of rubber powder were added to obtain rubber asphalt; the shear rate was 4000 r / min, and the shear time was 45 min; then, 0.6 parts of the rubber asphalt VOCs inhibitor based on MOFs material obtained in Example 1 was added to the rubber asphalt for high-speed shearing, and the temperature was kept at 170°C during the shearing process; after the shearing was completed, smoke-suppressing rubber asphalt was obtained; wherein the shear rate was 6000 r / min, and the shear time was 20 min.

[0083] Example 5 Smoke Suppression Rubber Asphalt 2

[0084] The smoke-suppressing rubber asphalt comprises 81.4 parts of 70# base asphalt, 18 parts of rubber powder, and 0.6 parts of the rubber asphalt VOCs inhibitor of the MOFs material obtained in Example 2, and is obtained specifically according to the following method:

[0085] 81.4 parts of base asphalt are heated to 160°C and kept warm with stirring. During the stirring process, 18 parts of rubber powder are added to obtain rubber asphalt; the shear rate is 6000 r / min, and the shear time is 40 min; then, 0.6 parts of the rubber asphalt VOCs inhibitor based on MOFs material described in Example 2 is added to the rubber asphalt for high-speed shearing, and the temperature is kept at 170°C during the shearing process; after the shearing is completed, smoke-suppressing rubber asphalt is obtained; wherein, the shear rate is 6000 r / min, and the shear time is 30 min.

[0086] Example 6 Smoke Suppression Rubber Asphalt 3

[0087] The smoke-suppressing rubber asphalt includes 77.4 parts of 70# base asphalt, 22 parts of rubber powder, and 0.6 parts of the rubber asphalt VOCs inhibitor of the MOFs material obtained in Example 3, and is specifically prepared according to the following method:

[0088] 77.4 parts of base asphalt are heated to 160°C and kept warm with stirring. During the stirring process, 22 parts of rubber powder are added to obtain rubber asphalt; the shear rate is 8000 r / min, and the shear time is 40 min; then, 0.6 parts of the rubber asphalt VOCs inhibitor based on MOFs material described in Example 3 is added to the rubber asphalt for high-speed shearing, and the temperature is kept at 170°C during the shearing process; after the shearing is completed, smoke-suppressing rubber asphalt is obtained; wherein, the shear rate is 8000 r / min, and the shear time is 30 min.

[0089] Gas chromatography-mass spectrometry (GC-MS) was used to quantitatively analyze and characterize the VOCs release of ordinary rubber asphalt and smoke-suppressing rubber asphalt based on MOFs materials prepared in Examples 4-6. Ordinary rubber asphalt and the above-mentioned Examples 4-6 were placed in heatable sealed containers, respectively, and the heating temperature was set to 170°C. After heating for 30 minutes, two gases were collected using gas collection bags and sent to GC-MS to detect VOCs content to evaluate the effect of rubber asphalt VOCs inhibitor based on MOFs materials on rubber powder VOCs inhibition. The test results are shown in Table 2. Figure 2 and Figure 3 shown.

[0090] Table 2

[0091] sample <![CDATA[VOCs concentration (mg / m 3 )]]> Ordinary rubber asphalt 845.94 Example 4 487.82 Example 5 243.67 Example 6 89.53

[0092] As shown in Table 2, for common rubber asphalt, Examples 4, 5, and 6, the total VOCs concentrations are 845.94, 487.82, 253.47, and 89.53 mg / m 3 It can be calculated that the inhibition rates of VOCs in Examples 4, 5 and 6 for rubber asphalt are as high as 42.3%, 71.2% and 89.4% respectively. Among them, the inhibition effect of Example 6 is the most significant, mainly due to its higher specific surface area.

[0093] Among the more than 100 volatile organic compounds in asphalt, four Class I carcinogens were detected, namely 1,3-butadiene, benzene, trichloroethylene and 1,2-dichloropropane.

[0094] Depend on Figure 2 It can be seen that compared with ordinary rubber asphalt, in Examples 4, 5, and 6, the concentrations of 1,3-butadiene were reduced by 44.8%, 74.9%, and 92.4%, respectively; the concentrations of benzene were reduced by 48.5%, 65.0%, and 90.1%, respectively; the concentrations of trichloroethylene were reduced by 38.5%, 66.3%, and 84.1%, respectively; the concentrations of 2-dichloropropane were reduced by 58.0%, 72.0%, and 89.4%, respectively, among which Example 6 had the best inhibitory effect on the four Class I carcinogens.

[0095] Depend on Figure 3 It can be seen that aliphatic hydrocarbons are the main components of VOCs. For ordinary rubber asphalt, Examples 4, 5, and 6, their contents are 46.0%, 54.9%, 56.8%, and 60.0%, respectively. The aromatic hydrocarbon content is the lowest, which are 5.7%, 7.8%, 5.4%, and 10.0%, respectively. With the addition of the rubber asphalt VOCs inhibitor based on the MOFs material, the number of asphalt VOCs decreases. For Examples 4, 5, and 6, the number decreases from 87 to 51, 37, and 20, respectively.

[0096] It can be calculated that compared with ordinary rubber asphalt, the aliphatic hydrocarbon concentration of the smoke-suppressing rubber asphalt in Examples 4, 5, and 6 is reduced by 30.0%, 47.5%, and 70.0%; the concentration of aromatic hydrocarbons is reduced by 20.0%, 60.0%, and 60.0%; the concentration of hydrocarbon derivatives is reduced by 50.0%, 63.6%, and 81.8%; the concentration of sulfur-containing compounds is reduced by 60.0%, 70.0%, and 90.0%; this shows that the rubber asphalt VOCs inhibitor based on MOFs material provided by the present invention can effectively adsorb a class of carcinogens and reduce the harm of a class of carcinogens to the human body.

[0097] In summary, the rubber asphalt VOCs inhibitor based on MOFs material provided by the present invention has a high specific surface area, controllable structure, and functional adsorption of specific functional group substances. The VOCs inhibition rate is as high as 89.4%, and the inhibition effect on a type of carcinogen is particularly significant, which can be as high as 92.4%.

[0098] It will be easily understood by those skilled in the art that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. Application of MOFs material in the preparation of rubber asphalt VOCs inhibitor, characterized in that: Used to absorb volatile organic compounds in rubber asphalt; The chemical formula of the MOFs material is C x H y O 32 Zr6, where x=84-120, y=52-76, is a zirconium-based metal organic framework material with a cubic crystal structure, a crystal pore size of 0.5-2 nm, and a specific surface area of ​​2000-3200 m 2 / g; and prepared according to the following method: Add zirconium chloride to N,N-dimethylformamide and stir at a constant temperature, add an organic ligand and acetic acid respectively, and stir at a constant temperature to obtain a mixed solution; The obtained mixed solution is reacted at 100-160° C. for 12-24 hours, and naturally cooled to room temperature after the reaction is completed; and washed with N, N-dimethylformamide and methanol, and centrifuged for multiple times to obtain a precipitate, and the precipitate is dried to obtain the MOFs material; The zirconium chloride, N,N-dimethylformamide, organic ligand and acetic acid are added in a molar ratio of 1:400-500:3-6:50-105 respectively; The organic ligand includes one or more combinations of 4,4'-biphenyldicarboxylic acid and 1,1':3',1"-terphenyl-4,4"-dicarboxylic acid.

2. The use of the MOFs material in the preparation of a rubber asphalt VOCs inhibitor as claimed in claim 1, characterized in that: The MOFs material has a crystal morphology size of 1 to 3 μm and a crystal pore size of 1 to 2 nm.

3. The use of the MOFs material in the preparation of a rubber asphalt VOCs inhibitor as claimed in claim 1, characterized in that: It is used to absorb 1,3-butadiene, benzene, trichloroethylene and 1,2-dichloropropane in volatile organic compounds of rubber asphalt.

4. A smoke-suppressing rubber asphalt, characterized in that: In terms of weight, it includes 70-90 parts of asphalt, 10-30 parts of rubber powder and 0.1-1 part of MOFs material; The chemical formula of the MOFs material is C x H y O 32 Zr6, where x=84-120, y=52-76, is a zirconium-based metal organic framework material with a cubic crystal structure, a crystal pore size of 0.5-2 nm, and a specific surface area of ​​2000-3200 m 2 / g; and prepared according to the following method: Add zirconium chloride to N,N-dimethylformamide and stir at a constant temperature, add an organic ligand and acetic acid respectively, and stir at a constant temperature to obtain a mixed solution; The obtained mixed solution is reacted at 100-160° C. for 12-24 hours, and naturally cooled to room temperature after the reaction is completed; and washed with N, N-dimethylformamide and methanol, and centrifuged for multiple times to obtain a precipitate, and the precipitate is dried to obtain the MOFs material; The zirconium chloride, N,N-dimethylformamide, organic ligand and acetic acid are added in a molar ratio of 1:400-500:3-6:50-105 respectively; The organic ligand includes one or more combinations of 4,4'-biphenyldicarboxylic acid and 1,1':3',1"-terphenyl-4,4"-dicarboxylic acid.

5. The smoke-suppressing rubber asphalt according to claim 4, characterized in that: Obtained according to the following preparation method: Take 70-90 parts of asphalt at 160°C to 170°C and 10-30 parts of rubber powder, mix and shear at a shear speed of 4000-8000 r / min and a shear time of 40-60 min to obtain rubber asphalt; 0.1 to 1 parts of MOFs material are added to the rubber asphalt for shearing, and the shear rate is 4000 to 8000 r / min, the shearing time is 20 to 40 min, and the temperature is kept at 160°C to 170°C during the shearing process; after the shearing is completed, smoke-suppressing rubber asphalt is obtained.

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