CN114437749A - Preparation method of amino-enriched asphalt and microspheres thereof - Google Patents
Preparation method of amino-enriched asphalt and microspheres thereof Download PDFInfo
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- C10C3/00—Working-up pitch, asphalt, bitumen
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Abstract
The invention discloses a preparation method of amino-enriched asphalt and microspheres thereof. The method comprises the steps of firstly, reacting polycyclic aromatic hydrocarbon with organic polycyclic amine compounds in an acidic organic solvent system to prepare amino-enriched asphalt, and then preparing the amino-enriched asphalt into a micron-sized spherical material. The amino-enriched asphalt and the amino-enriched asphalt microsphere prepared by the method have high amino content and high nitrogen content, can effectively improve the economic value of asphalt and broaden the application field of the asphalt.
Description
Technical Field
The invention relates to the technical field of asphalt materials, in particular to modified asphalt materials.
Background
The asphalt is a black-brown complex mixture composed of hydrocarbons with different molecular weights and nonmetal derivatives thereof, and can be divided into petroleum asphalt, coal tar asphalt and natural asphalt, wherein the petroleum asphalt is residue after crude oil distillation, the coal tar asphalt is residue during coal tar primary distillation, and the natural asphalt is petroleum asphalt in which petroleum exists in a natural form under the action of nature. Although asphalt has good waterproof, anti-corrosion and adhesive effects, is abundant in reserves and low in price, various kinds of asphalt generally contain some polycyclic aromatic compounds which are harmful to human bodies and environment, so that the direct use of the asphalt is greatly limited.
On the other hand, the pitch has the characteristics of high carbonization yield and the like, and can be used for preparing various carbon materials, such as activated carbon, porous carbon, carbon microspheres, carbon foam, mesocarbon microspheres, two-dimensional nano carbon materials, carbon fibers, electrode needle coke, C/C composite materials, graphite and the like, and the carbon materials show great potential in the fields of energy storage, hydrogen storage, catalysis, adsorption separation and the like, so that the pitch is further prepared into the carbon materials, the resources can be reasonably and effectively utilized at low level, the environmental pollution is reduced, and the economic value of the pitch can be obviously improved.
In the prior art, asphalt is mostly prepared into a carbon material through a direct carbonization process, and the prepared carbon material can only be obtained by further performing complex modification on products with more functional requirements.
Disclosure of Invention
One of the purposes of the invention is to provide a preparation method of amino-enriched asphalt, which can prepare a new asphalt material rich in amino, and the material can effectively reduce the harmfulness of asphalt and broaden the application field of the asphalt material.
The invention also aims to provide a preparation method of the amino-enriched asphalt microsphere, and the obtained microsphere material has higher economic and application values, can further obtain a high-nitrogen-doped carbon material, and has great application prospects in the fields of energy storage, hydrogen storage, catalysis, adsorption separation and the like.
The invention also aims to provide the amino-enriched asphalt microsphere material prepared by the preparation method of the amino-enriched asphalt microsphere.
In order to achieve one of the above purposes, the invention firstly provides the following technical scheme:
the amino-enriched asphalt comprises polycyclic aromatic hydrocarbon and/or a product of polycyclic aromatic hydrocarbon-containing asphalt and organic polycyclic amine compounds which are reacted in an acidic organic solvent system.
A preparation method of amino-enriched asphalt comprises the following steps: polycyclic aromatic hydrocarbon and/or asphalt containing polycyclic aromatic hydrocarbon react with organic polycyclic amine compounds in an acidic organic solvent system.
According to some embodiments of the invention, the asphalt may be any one or more of petroleum asphalt, coal tar asphalt, and natural asphalt.
According to some embodiments of the present invention, the product amino-enriched pitch may be further separated, extracted, purified, etc. after the reaction.
According to some embodiments of the present invention, the purification can be performed by performing a preliminary separation and purification on the product of the amino-enriched asphalt at 100-.
The inventor finds that the polycyclic aromatic hydrocarbon has an electron-rich structure, is easily oxidized into ketone, phenol, ester, carboxylic acid and the like under high-temperature acidic conditions, and can obtain the amino-enriched asphalt after further reaction with organic polycyclic amine which is easily protonated. Elemental analysis has shown that the amino-enriched bitumen of the present invention has an N content of 10% to 20%, such as 10.5%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 19.5% and any value in between.
Examples of the term "amino" used in the present invention include an amino group or an amine group such as a primary amine, a secondary amine or a tertiary amine.
In the art, the nitrogen content of the asphalt is more than 10%, which can be called as enrichment, and the amino-enriched asphalt in the invention refers to the asphalt containing amino with the nitrogen content of more than 10%.
In the present invention, the term Polycyclic Aromatic Hydrocarbons (PAHs) refers to Hydrocarbons having two or more benzene rings in the molecule. It mainly comprises one or more of the following components:
naphthalene, acenaphthylene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo (a) anthracene, chrysene, benzo (b) fluoranthene, benzo (k) fluoranthene, benzo (a) pyrene, indeno (1,2,3-cd) pyrene, dibenzo (a, h) anthracene, benzo (g, h, i) perylene, 1-methylnaphthalene and 2-methylnaphthalene.
According to some embodiments of the invention, the polycyclic aromatic hydrocarbon is selected from one or more of the group consisting of C9-C30 fused ring aromatic hydrocarbons.
According to some embodiments of the invention, the polycyclic aromatic hydrocarbon is selected from one or more of naphthalene, acenaphthylene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo (a) anthracene, chrysene, benzo (b) fluoranthene, benzo (k) fluoranthene, benzo (a) pyrene, indeno (1,2,3-cd) pyrene, dibenzo (a, h) anthracene, benzo (g, h, i) perylene, 1-methylnaphthalene, and 2-methylnaphthalene.
According to some embodiments of the invention, the organic polycyclic amine based compound is selected from one or more of hexamethylenetetramine, triethylenediamine, diethylenetriamine, hexamethyleneimine, triethylenediamine and cyclohexylamine, preferably Hexamethylenetetramine (HMTA).
According to some embodiments of the invention, the acidic organic solvent system consists of an organic solvent and an organic carboxylic acid.
According to some embodiments of the invention, the organic solvent is selected from one or more of N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide, preferably N-methylpyrrolidone.
According to some embodiments of the invention, the organic carboxylic acid is selected from one or more of glacial acetic acid, glycolic acid, citric acid and formic acid, preferably glacial acetic acid.
According to some embodiments of the invention, the molar ratio of the polycyclic aromatic hydrocarbon and/or the polycyclic aromatic hydrocarbon-containing bitumen to the organic polycyclic amine compound is 1 (0.5-5), such as 1:1, 1:1.5, 1:2.0, 1:2.5, 1:3.5, 1:4.0, 1:4.5 and any value in between.
According to some preferred embodiments of the present invention, the molar ratio of the polycyclic aromatic hydrocarbon and/or the polycyclic aromatic hydrocarbon-containing asphalt to the organic polycyclic amine compound is 1 (1.5-3).
According to some embodiments of the invention, the mass ratio of the polycyclic aromatic hydrocarbon and/or the polycyclic aromatic hydrocarbon-containing asphalt to the organic polycyclic amine compound is 1 (0.01-5), such as 1:0.7, 1:1, 1:1.5, 1:2.0, 1:2.5, 1:3.5, 1:4.0, 1:4.5, and any value therebetween.
According to some embodiments of the invention, the mass ratio of the polycyclic aromatic hydrocarbon and/or the polycyclic aromatic hydrocarbon-containing asphalt to the organic polycyclic amine compound is 1 (0.5-3).
According to some embodiments of the invention, the molar ratio of the polycyclic aromatic hydrocarbon and/or the polycyclic aromatic hydrocarbon-containing asphalt to the organic carboxylic acid is 1 (0.01-0.5), such as 1:0.05, 1:0.10, 1:0.12, 1:0.15, 1:0.25, 1:0.30, 1:0.35, 1:0.40, 1:0.45, and any value therebetween.
According to some embodiments of the invention, the molar ratio of the polycyclic aromatic hydrocarbon and/or the polycyclic aromatic hydrocarbon-containing bitumen to the organic carboxylic acid is 1 (0.05-0.2).
According to some embodiments of the invention, the mass ratio of the polycyclic aromatic hydrocarbon and/or the polycyclic aromatic hydrocarbon-containing asphalt to the organic carboxylic acid is 1: (0.001-0.5), such as 1:0.03, 1:0.05, 1:0.07, 1:0.09, 1:0.15, 1:0.20, 1:0.25, 1:0.30, 1:0.35, 1:0.40, 1:0.45, and any value in between.
According to some embodiments of the invention, the mass ratio of the polycyclic aromatic hydrocarbon and/or the polycyclic aromatic hydrocarbon-containing asphalt to the organic carboxylic acid is 1 (0.01-0.1).
According to some embodiments of the invention, the temperature of the reaction is 100-,
according to some embodiments of the invention, the reaction is carried out under an inert atmosphere.
In order to achieve the second purpose, the invention further provides a preparation method of the amino-enriched asphalt microsphere, which comprises the following steps:
(1) preparing amino-enriched asphalt;
(2) dissolving the obtained amino-enriched asphalt in a first solvent to obtain a precursor solution;
(3) dispersing the precursor solution in a second solvent, and heating the mixed system formed by the precursor solution until the first solvent contained in the mixed system is completely volatilized.
Step (1) in this embodiment may be implemented by any of the methods for producing amino-enriched bitumen described above or specific or preferred embodiments thereof.
The inventors surprisingly found that the amino-enriched asphalt can be further prepared into microsphere materials with uniform and regular shapes by the preparation method, so that the economic and application values of the amino-enriched asphalt can be further improved.
According to some embodiments of the present invention, some other optimized means may be added in step (2) and/or (3), such as adding mechanical, electrical, optical, magnetic, acoustic, and other auxiliary dispersing means, specifically, using a mechanical stirrer, a magnetic stirrer, an ultrasonic disperser, an electromagnetic stirrer, and other apparatuses having dispersing function during the process of forming the precursor solution and/or evaporating the solvent.
According to some embodiments of the invention, an ultrasonic atomizer with a vibration frequency of 10 to 30kHz and a power of 10 to 500W is used during the dispersion of the precursor in the second solvent.
According to some embodiments of the present invention, the precursor solution is mechanically stirred during the dispersion in the second solvent, and the stirring rate is preferably 300-.
According to some embodiments of the present invention, other auxiliary agents may be further added in step (2), such as a dispersant, an emulsifier, a thickener, a defoamer, and the like, during the formation of the precursor solution and/or the evaporation of the solvent.
Further, it is understood that although the present invention proposes heating the mixed system until the first solvent contained therein is completely volatilized, a person skilled in the art may also select other technical means comprehensively for the purpose of completely volatilizing the first solvent, such as quickly freezing the system and then subliming the solvent, cooling the system and then heating the system, heating the system and then cooling the system, etc., which should be considered to be included in the spirit of the present invention.
According to some embodiments of the invention, the first solvent is a good solvent for the amino-enriched pitch, preferably selected from one or more of water, ethanol, methanol, ethylene glycol, propylene glycol, acetone.
According to some embodiments of the invention, the second solvent is a poor solvent for the amino-enriched bitumen, preferably selected from one or more of vacuum pump oil, silicone oil, vegetable oil.
In the above specific embodiment, the good solvent is a solvent having a strong dissolving capacity for the amino-enriched asphalt and an interaction parameter χ thereof being less than 0.5; the poor solvent is a solvent with weak dissolving capacity to the amino-enriched asphalt and interaction parameter chi of the poor solvent is close to or greater than 0.5.
According to some embodiments of the present invention, the heating temperature of the mixed system is preferably in the range of the boiling point of the first solvent to 20 ℃ higher than the boiling point.
According to some embodiments of the present invention, in addition to the above steps (1) to (3), optionally, a step (4) of purifying the reaction mixture formed in step (3) may be further included.
According to some embodiments of the invention, step (4) comprises centrifuging the reaction mixture system and washing the resulting product multiple times after the first solvent has evaporated completely and cooled to room temperature.
According to some embodiments of the invention, the washing agent is preferably one or more of a C6-C9 alkane.
According to some embodiments of the invention, a surfactant is also added to the precursor solution.
Preferably, the surfactant is selected from one or more of coco glucoside, lauryl glucoside, cetearyl glucoside, glyceryl monostearate, sucrose ester, span and tween.
According to some embodiments of the invention, the mass ratio of the amino-enriched bitumen to the surfactant is 1 (0.01-0.5), such as 1:0.05, 1:0.12, 1:0.15, 1:0.25, 1:0.30, 1:0.35, 1:0.45 and any value in between.
According to some embodiments of the invention, the mass ratio of the amino-enriched bitumen to the surfactant is 1 (0.1-0.4).
According to some embodiments of the invention, the mass ratio of the amino-enriched bitumen to the first solvent is 1 (1-50), such as 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:38, 1:45, and any value therebetween.
According to some embodiments of the invention, the mass ratio of the amino-enriched pitch to the first solvent is 1 (5-40).
According to some embodiments of the invention, the mass ratio of the amino-enriched bitumen to the second solvent is 1 (1-150), such as 1:10, 1:20, 1:35, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90, 1:100, 1:115, 1:125, 1:130, 1:140, and any value in between.
According to some embodiments of the invention, the mass ratio of the amino-enriched pitch to the second solvent is 1 (30-120).
To achieve the third objective, the present invention further provides a micron-sized amino asphalt microsphere, which can be prepared by any one of the above methods for preparing amino-enriched asphalt microspheres, or specific, preferred embodiments thereof.
According to some embodiments of the present invention, the micro-sized amino asphalt microspheres have a diameter distribution of 1 to 20 μm.
According to some embodiments of the present invention, the nitrogen content of the micro-sized amino asphalt microsphere is 10% to 20%.
The invention has the following beneficial effects:
(1) the preparation method has the advantages of simple process, high balling rate, controllable conditions and easy large-scale preparation.
(2) The amino-enriched asphalt and the amino-enriched asphalt microsphere prepared by the invention introduce high-content amino into the asphalt material. The nitrogen atom contained in the amino group is close to the carbon atom structure, so that the material structure can not be obviously distorted in the process of substituting the carbon atom in the carbon skeleton as the heteroatom, and the structure of the carbon material can be further adjusted and the surface property of the material can be changed. Such as causing many dislocations, bends, dislocations, etc. with unpaired electron defect sites in the planar layer of graphitic crystallites in the carbon layer. Therefore, the invention not only effectively reduces the harmfulness of the asphalt through amino modification, but also can further expand the application field of the material.
(3) The amino-enriched asphalt microsphere is a micron-sized spherical material, can be used as an efficient Oxygen Reduction Reaction (ORR) electrocatalyst, an electrochemical capacitor, a lithium ion battery, an adsorbent, a catalyst carrier and the like by combining the characteristic of being rich in amino, and has high economic and application values.
(4) The amino-enriched asphalt microsphere can be processed simply to obtain the nitrogen-containing carbon material, and has higher value and wider application in the fields of energy storage, hydrogen storage, catalysis and adsorption, oral administration of medicines, blood purification, military protection, chromatographic columns and the like compared with pure carbon materials.
(5) The amino-enriched asphalt microsphere is prepared by directly reacting polycyclic aromatic hydrocarbon with organic polycyclic amine compounds, and a modified high-nitrogen carbon product can be obtained after carbonization. Compared with the traditional mode of firstly carbonizing and then modifying to obtain a modified carbon product, the method greatly reduces the complexity of reaction (the modification process of the carbonized product is generally complex and difficult), improves the content of other components in the modified product and the strength and stability of the combination of the components and carbon, reduces the production cost and improves the product quality.
(6) The preparation method and the product of the invention can effectively improve the utilization value and the economic value of the asphalt, effectively improve the utilization rate of resources and reduce the environmental hazard.
Drawings
Fig. 1 is an optical photograph of micron-sized amino-enriched asphalt microspheres prepared in example 1 of the present invention.
FIG. 2 is an IR spectrum of amino-enriched asphalt prepared in example 1 of the present invention.
FIG. 3 is a C-nuclear magnetic spectrum of the amino-enriched asphalt prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in detail with reference to the following embodiments and examples. It should be understood that the embodiments and examples described herein are only for illustrating and explaining the present invention and are not to be construed as limiting the present invention.
Example 1
Dissolving 0.1mol naphthalene and 0.2mol HMTA in 300mL N-methyl pyrrolidone, slowly dropping 0.01mol glacial acetic acid, and heating at 200 deg.C and N2The reaction was stirred under an atmosphere for 5 hours and then cooled to room temperature. The product was isolated and purified using a 180 ℃ rotary vacuum evaporator. And further purifying the separated and purified product in a vacuum oven at 160 ℃ for 10 hours to obtain the amino-enriched asphalt.
Weighing 1g of amino-enriched asphalt and 0.2g of span 80, dissolving in 10g of ethanol solution, and performing ultrasonic treatment for 30min until the asphalt is completely dissolved to obtain a precursor solution. And (3) blending the precursor solution with 60g of pump oil, and carrying out ultrasonic treatment for 30min until the precursor solution is uniformly dispersed. Then the system is magnetically stirred for 1 hour at the room temperature at the rotating speed of 500r/min, then the temperature is raised to 85 ℃, the temperature is kept for 4 hours, the ethanol is completely volatilized, then the heating is stopped, and the temperature is reduced to the room temperature. And then transferring the mixture to a centrifugal tube for centrifugal separation (5000r/min, 8min), and washing with n-hexane for multiple times to obtain the product, namely the amino-enriched asphalt microsphere. It can be further stored in n-hexane solution.
The obtained amino-enriched asphalt microsphere is shown in figure 1, and has yellow brown color, regular shape, and particle size distribution of 1-20 μm. In addition, infrared spectrum test is carried out on the product of the amino-enriched asphalt, as shown in figure 2, the product successfully introduces amine components on hydrocarbon, and the nitrogen content in the obtained amino-enriched asphalt microsphere is 19.18 percent according to an element analysis method test.
Example 2
Dissolving 0.1mol of pyrene and 0.2mol of HMTA in 300mL of N-methylpyrrolidone, slowly dropping 0.01mol of glacial acetic acid, and heating at 200 ℃ and N2Stirring and reacting for 5 hours under the protection of atmosphere, then cooling to room temperature, and aligning the product by using a 180 ℃ rotary vacuum evaporatorAnd (5) separating and purifying. And further purifying the separated and purified product in a vacuum oven at 160 ℃ for 10 hours to obtain the amino-enriched asphalt.
Weighing 2g of amino-enriched asphalt and 0.2g of span 60, dissolving in 10g of ethanol solution, and carrying out ultrasonic treatment for 30min until the asphalt is completely dissolved to obtain a precursor solution. The precursor solution is mixed with 60g of edible oil, ultrasonic treatment is carried out for 30min until the mixture is uniformly dispersed, and magnetic stirring is carried out for 1 hour at the rotating speed of 500r/min at room temperature. Then heating to 85 deg.C, keeping the temperature for 4 hr to volatilize ethanol completely, stopping heating, and cooling to room temperature. And then transferring the mixture to a centrifugal tube for centrifugal separation (5000r/min, 8min), and washing the mixture for multiple times by using normal hexane to obtain the product, namely the amino-enriched asphalt microsphere. It can be further stored in n-hexane solution.
The obtained amino-enriched asphalt microsphere is yellow brown, has regular shape and particle size distribution of 1-20 μm. And infrared spectrum test is carried out on the product of the amino-enriched asphalt, tests show that amine components are successfully introduced into hydrocarbon, and the nitrogen content in the obtained amino-enriched asphalt microspheres is 18.6% according to an element analysis method.
Example 3
Dissolving 0.1mol of 1-methylnaphthalene and 0.2mol of HMTA in 300mL of N-methylpyrrolidone, slowly dropping 0.01mol of glacial acetic acid, and heating at 200 ℃ under the action of N2The reaction was stirred for 5 hours under the protection of atmosphere, then cooled to room temperature, and the product was isolated and purified by a 180 ℃ rotary vacuum evaporator. And further purifying the separated and purified product in a vacuum oven at 160 ℃ for 10 hours to obtain the amino-enriched asphalt.
Weighing 1g of amino-enriched asphalt and 0.2g of Tween 80, dissolving in 10g of methanol solution, and performing ultrasonic treatment for 30min until the asphalt is completely dissolved to obtain a precursor solution. The precursor solution is mixed with 60g of pump oil, ultrasonic treatment is carried out for 30min until the dispersion is uniform, and magnetic stirring is carried out for 1 hour at the rotating speed of 500r/min at room temperature. Then heating to 85 deg.C, keeping the temperature for 4 hr to volatilize ethanol completely, stopping heating, and cooling to room temperature. And then transferring the mixture to a centrifugal tube for centrifugal separation (5000r/min, 8min), and washing with n-hexane for multiple times to obtain the product, namely the amino-enriched asphalt microsphere. It can be further stored in n-hexane solution.
The obtained amino-enriched asphalt microsphere is yellow brown, has regular shape and particle size distribution of 1-20 μm. And infrared spectrum test is carried out on the product of the amino-enriched asphalt, tests show that amine components are successfully introduced into hydrocarbon, and the nitrogen content in the obtained amino-enriched asphalt microspheres is 18.11% according to an element analysis method test.
Example 4
Dissolving 0.1mol of 2-methylnaphthalene and 0.2mol of HMTA in 300mL of N-methylpyrrolidone, slowly dropping 0.01mol of glacial acetic acid, and heating at 200 ℃ under the action of N2The reaction was stirred for 5 hours under the protection of atmosphere. And cooling to room temperature, separating and purifying the product by using a 180 ℃ rotary vacuum evaporator, and further purifying the separated and purified product in a 160 ℃ vacuum oven for 10 hours to obtain the amino-enriched asphalt.
Weighing 1g of amino-enriched asphalt and 0.2g of Tween 60, dissolving in 5g of methanol solution, and performing ultrasonic treatment for 30min until the asphalt is completely dissolved to obtain a precursor solution. The precursor solution is mixed with 60g of pump oil, ultrasonic treatment is carried out for 30min until the dispersion is uniform, and magnetic stirring is carried out for 1 hour at the rotating speed of 500r/min at room temperature. Then heating to 85 deg.C, keeping the temperature for 4 hr to volatilize ethanol completely, stopping heating, and cooling to room temperature. And then transferring the mixture to a centrifugal tube for centrifugal separation (5000r/min, 8min), and washing with n-hexane for multiple times to obtain the product, namely the amino-enriched asphalt microsphere. It can be further stored in n-hexane solution.
The obtained amino-enriched asphalt microsphere is yellow brown, has regular shape and particle size distribution of 1-20 μm. And infrared spectrum test is carried out on the product of the amino-enriched asphalt, tests show that amine components are successfully introduced into hydrocarbon, and the nitrogen content in the obtained amino-enriched asphalt microspheres is 18.01 percent according to an element analysis method test.
Example 5
Dissolving 0.1mol of anthracene and 0.2mol of HMTA in 300mL of N-methylpyrrolidone, slowly dropping 0.01mol of glacial acetic acid, and heating at 200 ℃ and N2The reaction was stirred for 5 hours under the protection of atmosphere, then cooled to room temperature, and the product was isolated and purified by a 180 ℃ rotary vacuum evaporator. The separated and purified product is further purified in a vacuum oven at 160 ℃ for 10 hoursAnd obtaining the amino-enriched asphalt.
Weighing 1g of amino-enriched asphalt and 0.3g of Tween 20, dissolving in 5g of acetone solution, and performing ultrasonic treatment for 30min until the asphalt is completely dissolved to obtain a precursor solution. And (3) blending the precursor solution with 60g of pump oil, carrying out ultrasonic treatment for 30min until the mixture is uniformly dispersed, and magnetically stirring the mixture for 1 hour at the room temperature at the rotating speed of 500 r/min. Then heating to 85 deg.C, keeping the temperature for 4 hr to volatilize ethanol completely, stopping heating, and cooling to room temperature. And then transferring the mixture to a centrifugal tube for centrifugal separation (5000r/min, 8min), and washing with n-hexane for multiple times to obtain the product, namely the amino-enriched asphalt microsphere. It can be further stored in n-hexane solution.
The obtained amino-enriched asphalt microsphere is yellow brown, has regular shape and particle size distribution of 1-20 μm. And infrared spectrum test is carried out on the product of the amino-enriched asphalt, tests show that amine components are successfully introduced into hydrocarbon, and the nitrogen content in the obtained amino-enriched asphalt microspheres is 15.29 percent according to an element analysis method test.
Example 6
Dissolving 0.05mol of pyrene, 0.05mol of naphthalene and 0.2mol of HMTA in 300mL of N-methylpyrrolidone, slowly dropping 0.01mol of glacial acetic acid, and heating at 200 ℃ and N2The reaction was stirred for 5 hours under the protection of atmosphere, then cooled to room temperature, and the product was isolated and purified by a 180 ℃ rotary vacuum evaporator. And further purifying the separated and purified product in a vacuum oven at 160 ℃ for 10 hours to obtain the amino-enriched asphalt.
0.5g of amino-enriched asphalt and 0.2g of span 80 are weighed and dissolved in 20g of aqueous solution, and ultrasonic treatment is carried out for 30min until the asphalt is completely dissolved, so as to obtain precursor solution. And (3) blending the precursor solution with 60g of pump oil, carrying out ultrasonic treatment for 30min until the mixture is uniformly dispersed, and magnetically stirring the mixture for 1 hour at the room temperature at the rotating speed of 500 r/min. Then heating to 110 deg.C, keeping the temperature for 4 hours to make the ethanol completely volatilize, stopping heating, and cooling to room temperature. And then transferring the mixture to a centrifugal tube for centrifugal separation (5000r/min, 8min), and washing with n-hexane for multiple times to obtain the product, namely the amino-enriched asphalt microsphere. It can be further stored in n-hexane solution.
The obtained amino-enriched asphalt microsphere is yellow brown, has regular shape and particle size distribution of 1-20 μm. And infrared spectrum test is carried out on the product of the amino-enriched asphalt, tests show that amine components are successfully introduced into hydrocarbon, and the nitrogen content in the obtained amino-enriched asphalt microspheres is 18.15% according to an element analysis method test.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. An amino-enriched asphalt comprises polycyclic aromatic hydrocarbon and/or a product of polycyclic aromatic hydrocarbon-containing asphalt and organic polycyclic amine compounds in an acidic organic solvent system.
2. A process for preparing the amino-enriched asphalt includes reaction between polycyclic aromatic hydrocarbon and/or the asphalt containing polycyclic aromatic hydrocarbon and organic polycyclic amine compound in acidic organic solvent system.
3. Amino-enriched pitch or process according to claim 1 or 2, wherein the polycyclic aromatic hydrocarbon is selected from one or more of C9-C30 fused ring aromatic hydrocarbons, preferably from one or more of naphthalene, acenaphthylene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo (a) anthracene, chrysene, benzo (b) fluoranthene, benzo (k) fluoranthene, benzo (a) pyrene, indeno (1,2,3-cd) pyrene, dibenzo (a, h) anthracene, benzo (g, h, i) perylene, 1-methylnaphthalene and 2-methylnaphthalene;
and/or the organic polycycloamine compound is selected from one or more of C4-C10 organic polycycloamine compounds, preferably from one or more of hexamethylene tetramine, triethylene diamine, diethylene triamine and cyclohexylamine.
4. The amino-enriched pitch or process according to any of claims 1-3, wherein the acidic organic solvent system comprises an organic solvent and an organic carboxylic acid; preferably, the organic solvent is selected from one or more of polar solvents, more preferably from one or more of N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide;
and/or the organic carboxylic acid is selected from one or more of C1-C6 organic carboxylic acids, preferably from one or more of glacial acetic acid, glycolic acid, citric acid and formic acid.
5. The amino-enriched asphalt or the method as claimed in any one of claims 1 to 4, wherein the molar ratio of the polycyclic aromatic hydrocarbon and/or the asphalt containing polycyclic aromatic hydrocarbon to the organic polycyclic amine compound is 1 (0.5-5), preferably 1 (1.5-3), and the mass ratio of the polycyclic aromatic hydrocarbon and/or the asphalt containing polycyclic aromatic hydrocarbon to the organic polycyclic amine compound is 1 (0.01-5), preferably 1 (0.5-3);
and/or the molar ratio of the polycyclic aromatic hydrocarbon and/or the polycyclic aromatic hydrocarbon-containing asphalt to the organic carboxylic acid is 1 (0.01-0.5), preferably 1 (0.05-0.2), and the mass ratio of the polycyclic aromatic hydrocarbon and/or the polycyclic aromatic hydrocarbon-containing asphalt to the organic carboxylic acid is 1 (0.001-0.5), preferably 1 (0.01-0.1);
and/or the temperature of the reaction is 100-250 ℃, preferably 150-200 ℃, preferably the reaction is carried out under an inert atmosphere.
6. A preparation method of amino-enriched asphalt microspheres comprises the following steps:
s1: dissolving the amino-enriched pitch of any of claims 1-4 or the amino-enriched pitch prepared according to the process of any of claims 1-4 in a first solvent to obtain a precursor solution;
s2: dispersing the precursor solution in a second solvent to form a mixed system;
s3: heating the mixed system obtained in the step S2 to completely volatilize the first solvent to form a reaction mixture;
and optionally, step S4: the reaction mixture formed in step S3 was purified.
7. The method of claim 6, wherein: the first solvent is a good solvent for the amino-enriched asphalt, preferably the first solvent is selected from one or more of water, C1-C6 alcohol and C3-C6 ketone, preferably one or more of water, ethanol, methanol, ethylene glycol, propylene glycol and acetone;
and/or the second solvent is a poor solvent for the amino-enriched asphalt, preferably the second solvent is selected from one or more of vacuum pump oil, silicone oil and vegetable oil;
and/or the precursor solution also comprises a surfactant; preferably, the surfactant is selected from one or more of coco glucoside, lauryl glucoside, cetearyl glucoside, glycerol monostearate, sucrose esters, span and tween.
8. The production method according to claim 6 or 7, characterized in that: the mass ratio of the amino-enriched asphalt to the surfactant is 1 (0.01-0.5), preferably 1 (0.1-0.4);
and/or the mass ratio of the amino-enriched asphalt to the first solvent is 1 (1-50), preferably 1 (5-40);
and/or the mass ratio of the amino-enriched pitch to the second solvent is 1 (1-150), preferably 1 (30-120).
9. Micron-sized amino-bituminous microspheres, prepared by a method according to any one of claims 6 to 8, preferably having a diameter distribution of 1 to 20 μm and/or a nitrogen content of 10% to 20%.
10. The use of micro-sized amino asphalt microspheres according to claim 9 in the fields of energy storage, hydrogen storage, catalysis and adsorptive separation.
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