阅读说明：本技术 一种改性环保沥青的制备方法 (Preparation method of modified environment-friendly asphalt ) 是由 郭丽 孙传洪 于 2020-11-19 设计创作，主要内容包括：本发明公开了一种改性环保沥青的制备方法,涉及沥青材料技术领域。本发明先将嵌段共聚物与改性二氧化硅混炼,得改性嵌段共聚物,然后将基料与废胶粉混合,并加入改性嵌段共聚物和古马隆树脂,搅拌反应,得坯料,最后,将坯料与醛类化合物混合,并加入促进剂,于惰性气体条件下搅拌反应后,得改性环保沥青。本发明制备的改性环保沥青具有优异的低温抗裂性能,且有害物质释放量较少,复合环保的要求。(The invention discloses a preparation method of modified environment-friendly asphalt, and relates to the technical field of asphalt materials. Firstly, mixing a block copolymer and modified silicon dioxide to obtain a modified block copolymer, then mixing a base material and waste rubber powder, adding the modified block copolymer and coumarone resin, stirring and reacting to obtain a blank, finally, mixing the blank and an aldehyde compound, adding an accelerant, and stirring and reacting under the condition of inert gas to obtain the modified environment-friendly asphalt. The modified environment-friendly asphalt prepared by the invention has excellent low-temperature crack resistance, less release amount of harmful substances and meets the requirement of environmental protection.)

1. The preparation method of the modified environment-friendly asphalt is characterized by mainly comprising the following preparation steps:

(1) mixing the block copolymer and the modified silicon dioxide in an internal mixer, mixing, and discharging to obtain a modified block copolymer;

(2) mixing a base material and waste rubber powder, adding the modified block copolymer obtained in the step (1) and coumarone resin, and stirring to react to obtain a blank;

(3) mixing the blank obtained in the step (2) with an aldehyde compound, adding an accelerant, and stirring and reacting under the condition of inert gas to obtain the modified environment-friendly asphalt;

(4) and (4) carrying out index analysis on the modified environment-friendly asphalt obtained in the step (3).

2. The preparation method of the modified environment-friendly asphalt as claimed in claim 2, wherein the preparation method of the modified environment-friendly asphalt mainly comprises the following preparation steps:

(1) mixing a styrene-butadiene-styrene block copolymer and modified silicon dioxide according to the mass ratio of 20: 1-40: 1, mixing the materials in an internal mixer, mixing for 10-20 min at the temperature of 150-170 ℃ and the rotating speed of 60-80 r/min, and discharging to obtain a modified block copolymer;

(2) mixing a base material and waste rubber powder according to a mass ratio of 50: 1-60: 1, adding the modified block copolymer obtained in the step (1) with the mass of 0.05-0.12 time of that of the base material and coumarone resin with the mass of 0.01-0.05 time of that of the base material into a mixture of the base material and the waste rubber powder, and stirring and reacting for 2 hours at the temperature of 170-200 ℃ to obtain a blank;

(3) mixing the blank obtained in the step (2) with an aldehyde compound according to the mass ratio of 20: 1-40: 1, mixing, adding an accelerant with the mass of 0.01-0.02 times of that of the blank, and stirring and reacting for 5-10 hours in a nitrogen atmosphere to obtain modified environment-friendly asphalt;

(4) and (4) carrying out index analysis on the modified environment-friendly asphalt obtained in the step (3).

3. The method for preparing modified environment-friendly asphalt as claimed in claim 1, wherein the modified silica in step (1) is prepared by mixing organic bentonite, dodecylamine and tetraethoxysilane in a molar ratio of 1: 20: 150, adding cetyl trimethyl ammonium bromide which is 0.1-0.2 times of the mass of the organic bentonite, stirring for reacting for 4-5 hours, calcining for 1-3 hours at the temperature of 450-1000 ℃ to obtain pretreated silicon dioxide, and mixing the pretreated silicon dioxide with a silane coupling agent KH-550 in a mass ratio of 3: 1, mixing the mixture with ethanol, stirring and reacting to obtain aminated pretreated silicon dioxide, wherein the aminated pretreated silicon dioxide and glycidyl bromoisobutyrate are mixed according to the mass ratio of 100: 1, mixing the raw materials in water, stirring for reaction, filtering, washing and drying to obtain a modified silicon dioxide blank, wherein the modified silicon dioxide blank and cuprous bromide are mixed according to a mass ratio of 80: 1, mixing the mixture with anisole which is 10 times of the mass of a modified silicon dioxide blank, stirring and mixing the mixture, adding pentamethyl diethylenetriamine which is 0.1-0.2 times of the mass of the modified silicon dioxide blank and a styrene solution with the mass fraction of 10-40% which is 10 times of the mass of the modified silicon dioxide blank, stirring and reacting the mixture to obtain a mixture, mixing the mixture with methanol, filtering and drying the mixture to obtain the modified silicon dioxide.

4. The method for preparing modified environment-friendly asphalt according to claim 1, wherein the base material in the step (2) is one or more than two of aromatic heavy oil, coal asphalt and construction asphalt; the aromatic heavy oil is selected from one or two or more of coal tar, pitch coking heavy oil, wash oil, anthracene oil I, anthracene oil II or low-temperature dry distillation coal tar pitch.

5. The method for preparing modified environment-friendly asphalt according to claim 1, wherein the aldehyde compound in the step (3) is one or a combination of two of formaldehyde, trioxymethylene, paraformaldehyde, benzaldehyde, terephthalaldehyde, p-tolualdehyde, cinnamaldehyde and salicylaldehyde.

6. The method for preparing modified environment-friendly asphalt according to claim 1, wherein the accelerator in step (3) is any one of sulfonic acid, methanesulfonic acid, ethylsulfonic acid, benzenesulfonic acid or sulfamic acid.

Technical Field

The invention relates to the technical field of asphalt materials, in particular to a preparation method of modified environment-friendly asphalt.

Background

The coal tar pitch is the residue of coal tar after distillation and extraction of fractions (light oil, phenol oil, naphthalene oil, wash oil, anthracene oil and the like), is a thermoplastic material, has unique strong bonding capacity, carbon-rich low ash, excellent compatibility and affinity with solid carbonaceous materials, higher coking residual carbon value, easy graphitization of carbonized products, good infiltration and infiltration, low cost and easy acquisition, and is widely applied to industries such as aluminum smelting, steel making, carbon industry, refractory materials, building materials, road building and the like. Coal tar pitch contains more carcinogenic polycyclic aromatic hydrocarbon, particularly strong carcinogenic benzopyrene, which seriously harms human health and pollutes the environment, so the coal tar pitch is restricted in Europe in the nineties of the twentieth century in view of the requirement of environmental protection.

Since coal tar is found to be carcinogenic by Cook doctor in 1933, polycyclic aromatic hydrocarbons with 4-6 rings are confirmed to have different carcinogenicity, 15 polycyclic aromatic hydrocarbons are listed as carcinogenic aromatic hydrocarbons by the United states environmental protection agency, the emission control concentration of benzopyrene (BaP) which is the most important carcinogen in the polycyclic aromatic hydrocarbons is specified, Germany has the most strict regulation on benzopyrene (BaP) contained in coal tar, the allowable amount of BaP in technical products is not more than 50ppm, and the BaP content in coal tar is generally 1.5-2.5% (equivalent to 15000-25000 ppm), so that a plurality of applications of coal tar are practically cancelled, the strict requirements on environmental protection are met, and the prevention and treatment of coal tar pollution are urgent. At present, the method for reducing benzopyrene (BaP) in coal pitch mainly comprises the following steps: polymer modification, ozone-containing air oxidation, vacuum distillation, and ultraviolet irradiation. The invention provides a compound modification method to prepare environment-friendly asphalt.

Disclosure of Invention

The invention aims to provide a preparation method of modified environment-friendly asphalt, which aims to solve the problems in the background technology.

In order to achieve the purpose, the invention provides the following technical scheme:

the preparation method of the modified environment-friendly asphalt is characterized by mainly comprising the following preparation steps:

(1) mixing the block copolymer and the modified silicon dioxide in an internal mixer, mixing, and discharging to obtain a modified block copolymer;

(2) mixing a base material and waste rubber powder, adding the modified block copolymer obtained in the step (1) and coumarone resin, and stirring to react to obtain a blank;

(3) mixing the blank obtained in the step (2) with an aldehyde compound, adding an accelerant, and stirring and reacting under the condition of inert gas to obtain the modified environment-friendly asphalt;

(4) and (4) carrying out index analysis on the modified environment-friendly asphalt obtained in the step (3).

As optimization, the preparation method of the modified environment-friendly asphalt mainly comprises the following preparation steps:

(1) mixing a styrene-butadiene-styrene block copolymer and modified silicon dioxide according to the mass ratio of 20: 1-40: 1, mixing the materials in an internal mixer, mixing for 10-20 min at the temperature of 150-170 ℃ and the rotating speed of 60-80 r/min, and discharging to obtain a modified block copolymer;

(2) mixing a base material and waste rubber powder according to a mass ratio of 50: 1-60: 1, adding the modified block copolymer obtained in the step (1) with the mass of 0.05-0.12 time of that of the base material and coumarone resin with the mass of 0.01-0.05 time of that of the base material into a mixture of the base material and the waste rubber powder, and stirring and reacting for 2 hours at the temperature of 170-200 ℃ to obtain a blank;

(3) mixing the blank obtained in the step (2) with an aldehyde compound according to the mass ratio of 20: 1-40: 1, mixing the raw materials in a reaction kettle, adding an accelerant which is 0.01-0.02 times of the mass of the blank into the reaction kettle, introducing nitrogen into the reaction kettle at a speed of 50-200 mL/min, and stirring and reacting for 5-10 hours at the temperature of 120-16 ℃ to obtain the modified environment-friendly asphalt;

(4) and (4) carrying out index analysis on the modified environment-friendly asphalt obtained in the step (3).

Optimally, the preparation method of the modified silicon dioxide in the step (1) comprises the following steps of mixing organic bentonite, dodecylamine and tetraethoxysilane according to a molar ratio of 1: 20: 150, adding cetyl trimethyl ammonium bromide which is 0.1-0.2 times of the mass of the organic bentonite, stirring for reacting for 4-5 hours, calcining for 1-3 hours at the temperature of 450-1000 ℃ to obtain pretreated silicon dioxide, and mixing the pretreated silicon dioxide with a silane coupling agent KH-550 in a mass ratio of 3: 1, mixing the mixture with ethanol, stirring and reacting to obtain aminated pretreated silicon dioxide, wherein the aminated pretreated silicon dioxide and glycidyl bromoisobutyrate are mixed according to the mass ratio of 100: 1, mixing the raw materials in water, stirring for reaction, filtering, washing and drying to obtain a modified silicon dioxide blank, wherein the modified silicon dioxide blank and cuprous bromide are mixed according to a mass ratio of 80: 1, mixing the mixture with anisole which is 10 times of the mass of a modified silicon dioxide blank, stirring and mixing the mixture, adding pentamethyl diethylenetriamine which is 0.1-0.2 times of the mass of the modified silicon dioxide blank and a styrene solution with the mass fraction of 10-40% which is 10 times of the mass of the modified silicon dioxide blank, stirring and reacting the mixture to obtain a mixture, mixing the mixture with methanol, filtering and drying the mixture to obtain the modified silicon dioxide.

As optimization, the base material in the step (2) is one or more than two of aromatic heavy oil, coal tar pitch and construction asphalt; the aromatic heavy oil is selected from one or two or more of coal tar, pitch coking heavy oil, wash oil, anthracene oil I, anthracene oil II or low-temperature dry distillation coal tar pitch.

Preferably, the aldehyde compound in the step (3) is any one or a combination of two of formaldehyde, trioxymethylene, paraformaldehyde, benzaldehyde, terephthalaldehyde, p-tolualdehyde, cinnamaldehyde or salicylaldehyde.

Preferably, the accelerator in step (3) is any one of sulfonic acid, methanesulfonic acid, ethylsulfonic acid, benzenesulfonic acid or sulfamic acid.

Compared with the prior art, the invention has the beneficial effects that:

the modified silicon dioxide is added into the styrene-butadiene-styrene block copolymer during the preparation of the modified environment-friendly asphalt.

Firstly, the organic bentonite is added in the preparation process of the modified silicon dioxide, the ethyl orthosilicate can be hydrolyzed between the layers of the organic bentonite due to the existence of the organic bentonite, and a silicon dioxide supporting layer is formed, so that the modified silicon dioxide can be inlaid between the layers of the organic bentonite and has a porous silicon dioxide structure after being calcined, and after the modified silicon dioxide is added into a product, a lamellar mechanism of the bentonite can play a lubricating role, so that the asphalt and the styrene-butadiene-styrene block copolymer are better mixed, a part of harmful substances can be sealed due to the existence of the lamellar structure in the use process of the product, the environmental protection performance of the product is further improved, secondly, after the mesoporous silicon dioxide between the layers of the organic bentonite is treated, the surface of the mesoporous silicon dioxide is grafted with the polystyrene, after the modified silicon dioxide is mixed with the styrene-butadiene-styrene block copolymer, the modified silicon dioxide can be dispersed in styrene-butadiene-styrene block copolymer through polystyrene, and due to the existence of the structure among the organic bentonite layers, the mesoporous silicon dioxide has larger specific surface area, so that the mesoporous silicon dioxide plays a role in adsorbing harmful substances of asphalt in the asphalt, and further the environmental protection performance of the asphalt is further improved.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

In order to more clearly illustrate the method provided by the present invention, the following examples are used to illustrate the method for testing each index of the modified environment-friendly asphalt prepared in the following examples as follows:

softening point test: the softening points of the modified environment-friendly asphalts obtained in the examples and the comparative examples were measured.

Content of harmful substances: the contents of benzopyrene and aldehyde compounds in the modified environment-friendly asphalt obtained in each example and each comparative example are measured.

Low temperature crack resistance test

And (3) according to the test regulations of the asphalt and the asphalt mixture for highway engineering, evaluating the low-temperature crack resistance of the warm-mixed asphalt mixture by adopting a low-temperature bending failure test. The rolled rut plate is cut into specified sizes, the length is 250mm +/-2.0 mm, the width is 30mm +/-2.0 mm, and the height is 35mm +/-2.0 mm. Placing the test piece in an environment box with the temperature of minus 10 +/-0.5 ℃ for 5 hours to ensure that the overall temperature of the test piece reaches minus 10 +/-0.5 ℃, placing the test piece on a support for loading, and testing the low-temperature crack resistance of the two asphalt mixtures

Example 1

The preparation method of the modified environment-friendly asphalt mainly comprises the following preparation steps:

(1) mixing a styrene-butadiene-styrene block copolymer and modified silicon dioxide according to the mass ratio of 30: 1, mixing the materials in an internal mixer, mixing for 15min at the temperature of 170 ℃ and the rotating speed of 60r/min, and discharging to obtain a modified block copolymer;

(2) mixing a base material and waste rubber powder according to a mass ratio of 50: 1, adding the modified block copolymer obtained in the step (1) with the mass of 0.08 time of that of the base material and coumarone resin with the mass of 0.01 time of that of the base material into a mixture of the base material and the waste rubber powder, and stirring and reacting for 2 hours at the temperature of 200 ℃ to obtain a blank;

(3) mixing the blank obtained in the step (2) with an aldehyde compound according to a mass ratio of 30: 1, mixing, adding an accelerant with the mass of 0.01 time of that of the blank, and stirring and reacting for 8 hours in a nitrogen atmosphere to obtain the modified environment-friendly asphalt;

(4) and (4) carrying out index analysis on the modified environment-friendly asphalt obtained in the step (3).

Optimally, the preparation method of the modified silicon dioxide in the step (1) comprises the following steps of mixing organic bentonite, dodecylamine and tetraethoxysilane according to a molar ratio of 1: 20: 150, adding hexadecyl trimethyl ammonium bromide with the mass of 0.1 time of that of the organic bentonite, stirring for reaction for 5 hours, calcining for 23 hours at the temperature of 800 ℃ to obtain pretreated silicon dioxide, and mixing the pretreated silicon dioxide with a silane coupling agent KH-550 in a mass ratio of 3: 1, mixing the mixture with ethanol, stirring and reacting to obtain aminated pretreated silicon dioxide, wherein the aminated pretreated silicon dioxide and glycidyl bromoisobutyrate are mixed according to the mass ratio of 100: 1, mixing the raw materials in water, stirring for reaction, filtering, washing and drying to obtain a modified silicon dioxide blank, wherein the modified silicon dioxide blank and cuprous bromide are mixed according to a mass ratio of 80: 1, mixing the mixture with anisole which is 10 times of the mass of the modified silicon dioxide blank, stirring and mixing the mixture, adding pentamethyl diethylenetriamine which is 0.1 times of the mass of the modified silicon dioxide blank and a styrene solution with the mass fraction of 20 percent which is 10 times of the mass of the modified silicon dioxide blank, stirring and reacting the mixture to obtain a mixture, mixing the mixture with methanol, filtering and drying the mixture to obtain the modified silicon dioxide.

Preferably, the base material in the step (2) is aromatic heavy oil and coal tar pitch according to a mass ratio of 1: 2, mixing; coal tar is used for the separation of the aromatic heavy oil.

Preferably, the aldehyde compound in the step (3) is formaldehyde.

Preferably, the accelerator in step (3) is methanesulfonic acid.

Example 2

The preparation method of the modified environment-friendly asphalt mainly comprises the following preparation steps:

(1) mixing a base material and waste rubber powder according to a mass ratio of 50: 1, adding modified silicon dioxide with the mass of 0.08 time of that of the base material and coumarone resin with the mass of 0.01 time of that of the base material into the mixture of the base material and the waste rubber powder, and stirring and reacting for 2 hours at the temperature of 200 ℃ to obtain a blank;

(2) mixing the blank obtained in the step (1) with an aldehyde compound according to a mass ratio of 30: 1, mixing, adding an accelerant with the mass of 0.01 time of that of the blank, and stirring and reacting for 8 hours in a nitrogen atmosphere to obtain the modified environment-friendly asphalt;

(3) and (3) carrying out index analysis on the modified environment-friendly asphalt obtained in the step (2).

Optimally, the preparation method of the modified silicon dioxide in the step (1) comprises the following steps of mixing organic bentonite, dodecylamine and tetraethoxysilane according to a molar ratio of 1: 20: 150, adding hexadecyl trimethyl ammonium bromide with the mass of 0.1 time of that of the organic bentonite, stirring for reaction for 5 hours, calcining for 23 hours at the temperature of 800 ℃ to obtain pretreated silicon dioxide, and mixing the pretreated silicon dioxide with a silane coupling agent KH-550 in a mass ratio of 3: 1, mixing the mixture with ethanol, stirring and reacting to obtain aminated pretreated silicon dioxide, wherein the aminated pretreated silicon dioxide and glycidyl bromoisobutyrate are mixed according to the mass ratio of 100: 1, mixing the raw materials in water, stirring for reaction, filtering, washing and drying to obtain a modified silicon dioxide blank, wherein the modified silicon dioxide blank and cuprous bromide are mixed according to a mass ratio of 80: 1, mixing the mixture with anisole which is 10 times of the mass of the modified silicon dioxide blank, stirring and mixing the mixture, adding pentamethyl diethylenetriamine which is 0.1 times of the mass of the modified silicon dioxide blank and a styrene solution with the mass fraction of 20 percent which is 10 times of the mass of the modified silicon dioxide blank, stirring and reacting the mixture to obtain a mixture, mixing the mixture with methanol, filtering and drying the mixture to obtain the modified silicon dioxide.

Preferably, the base stock in the step (1) is aromatic heavy oil and coal tar pitch in a mass ratio of 1: 2, mixing; coal tar is used for the separation of the aromatic heavy oil.

Preferably, the aldehyde compound in the step (2) is formaldehyde.

Preferably, the accelerator in step (2) is methanesulfonic acid.

Example 3

The preparation method of the modified environment-friendly asphalt mainly comprises the following preparation steps:

(1) mixing a styrene-butadiene-styrene block copolymer and modified silicon dioxide according to the mass ratio of 30: 1, mixing the materials in an internal mixer, mixing for 15min at the temperature of 170 ℃ and the rotating speed of 60r/min, and discharging to obtain a modified block copolymer;

(2) mixing a base material and waste rubber powder according to a mass ratio of 50: 1, adding the modified block copolymer obtained in the step (1) with the mass of 0.08 time of that of the base material and coumarone resin with the mass of 0.01 time of that of the base material into a mixture of the base material and the waste rubber powder, and stirring and reacting for 2 hours at the temperature of 200 ℃ to obtain a blank;

(3) mixing the blank obtained in the step (2) with an aldehyde compound according to a mass ratio of 30: 1, mixing, adding an accelerant with the mass of 0.01 time of that of the blank, and stirring and reacting for 8 hours in a nitrogen atmosphere to obtain the modified environment-friendly asphalt;

(4) and (4) carrying out index analysis on the modified environment-friendly asphalt obtained in the step (3).

Optimally, the preparation method of the modified silicon dioxide in the step (1) comprises the following steps of mixing organic bentonite, dodecylamine and tetraethoxysilane according to a molar ratio of 1: 20: 150, adding hexadecyl trimethyl ammonium bromide with the mass of 0.1 time of that of the organic bentonite, stirring for 5 hours after reaction, and calcining for 23 hours at the temperature of 800 ℃ to obtain the modified silicon dioxide.

Preferably, the base material in the step (2) is aromatic heavy oil and coal tar pitch according to a mass ratio of 1: 2, mixing; coal tar is used for the separation of the aromatic heavy oil.

Preferably, the aldehyde compound in the step (3) is formaldehyde.

Preferably, the accelerator in step (3) is methanesulfonic acid.

Comparative example

The preparation method of the modified environment-friendly asphalt mainly comprises the following preparation steps:

(1) mixing a base material and waste rubber powder according to a mass ratio of 50: 1, adding modified silicon dioxide with the mass of 0.08 time of that of the base material and coumarone resin with the mass of 0.01 time of that of the base material into the mixture of the base material and the waste rubber powder, and stirring and reacting for 2 hours at the temperature of 200 ℃ to obtain a blank;

(2) mixing the blank obtained in the step (1) with an aldehyde compound according to a mass ratio of 30: 1, mixing, adding an accelerant with the mass of 0.01 time of that of the blank, and stirring and reacting for 8 hours in a nitrogen atmosphere to obtain the modified environment-friendly asphalt;

(3) and (3) carrying out index analysis on the modified environment-friendly asphalt obtained in the step (2).

Optimally, the preparation method of the modified silicon dioxide in the step (1) comprises the following steps of mixing organic bentonite, dodecylamine and tetraethoxysilane according to a molar ratio of 1: 20: 150, adding hexadecyl trimethyl ammonium bromide with the mass of 0.1 time of that of the organic bentonite, stirring for 5 hours after reaction, and calcining for 23 hours at the temperature of 800 ℃ to obtain the modified silicon dioxide.

Preferably, the base stock in the step (1) is aromatic heavy oil and coal tar pitch in a mass ratio of 1: 2, mixing; coal tar is used for the separation of the aromatic heavy oil.

Preferably, the aldehyde compound in the step (2) is formaldehyde.

Preferably, the accelerator in step (2) is methanesulfonic acid.

Examples of effects

Table 1 below shows the results of performance analysis of the modified environment-friendly asphalt prepared by using examples 1 to 3 of the present invention and a comparative example.

TABLE 1

As can be seen from the comparison of the experimental data of example 1 and the comparative example in Table 1, the addition of the modified silica in the preparation of the modified environment-friendly asphalt can effectively improve the service performance of the product and make the product more environment-friendly.

It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.