CN114437398A - Amino-enriched asphalt hollow pellet and preparation method and application thereof - Google Patents

Amino-enriched asphalt hollow pellet and preparation method and application thereof Download PDF

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CN114437398A
CN114437398A CN202011205313.2A CN202011205313A CN114437398A CN 114437398 A CN114437398 A CN 114437398A CN 202011205313 A CN202011205313 A CN 202011205313A CN 114437398 A CN114437398 A CN 114437398A
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asphalt
amino
enriched
polycyclic aromatic
aromatic hydrocarbon
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CN114437398B (en
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王晓鹏
陈婧
王蔼廉
计文希
张韬毅
薛锐生
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/122—Pulverisation by spraying
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
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    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
    • C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
    • C—CHEMISTRY; METALLURGY
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    • C08J2395/00—Bituminous materials, e.g. asphalt, tar or pitch
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    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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Abstract

The invention discloses an amino-enriched asphalt hollow pellet and a preparation method thereof. The amino-enriched asphalt hollow bead is prepared by carrying out spray drying on amino-enriched asphalt, wherein the amino-enriched asphalt comprises polycyclic aromatic hydrocarbons and/or a product of reaction of the asphalt containing the polycyclic aromatic hydrocarbons and organic polycyclic amine compounds in an acidic organic solvent system. The amino-enriched asphalt and the amino-enriched asphalt hollow spheres 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

Amino-enriched asphalt hollow pellet and preparation method and application thereof
Technical Field
The invention relates to the technical field of asphalt materials, in particular to a modified asphalt material, and specifically relates to an amino-enriched asphalt hollow bead, and a preparation method and application thereof.
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 petroleum pitch is the residue after distillation of crude oil and pitch is a by-product of coking. The medium petrochemical industry is one of the largest oil refining enterprises in China and has rich asphalt resources. The pitch has the characteristics of abundant reserves, low price, high carbonization yield and the like, and is an irreplaceable raw material for preparing various carbon materials. The asphalt is prepared into 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, so that the economy of the asphalt is improved, resources can be reasonably and effectively utilized, and the environmental pollution is reduced. In addition, the carbon materials show great potential in the fields of energy storage, hydrogen storage, catalysis, adsorption separation and the like.
Nitrogen-doped carbon materials have received great attention as one of the most popular functional materials for their wide application, such as in the fields of electrocatalysts for Oxygen Reduction Reaction (ORR), electrochemical capacitors, lithium ion batteries, adsorbents, and catalyst carriers. In the periodic table of elements, the two elements of carbon and nitrogen are adjacent and have close structures, and the material structure can not be obviously distorted in the process of replacing carbon atoms in a carbon skeleton by nitrogen atoms. The heteroatom can modulate the structure of the carbon material and change the surface property of the material, so that the graphite microcrystal plane layer in the carbon layer generates a plurality of dislocations, bends, dislocation and the like with unpaired electronic defect sites; meanwhile, the heteroatom can form a local surface functional group, so that the surface of the carbon material has acidity and alkalinity. The nitriding effect of the nitrogen element thus gives the carbon material completely new properties.
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 an amino-enriched pitch hollow bead material, which 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 second purpose of the invention is to provide a preparation method of amino-enriched asphalt hollow pellets, which can prepare a new amino-enriched asphalt material, 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 the amino-enriched asphalt hollow spheres in CO2Application in the field of selective adsorption separation.
In order to achieve one of the above purposes, the invention firstly provides the following technical scheme:
the amino-enriched asphalt hollow bead is prepared by carrying out spray drying on amino-enriched asphalt, wherein the amino-enriched asphalt comprises polycyclic aromatic hydrocarbons and/or a product of reaction of the asphalt containing the polycyclic aromatic hydrocarbons and organic polycyclic amine compounds in an acidic organic solvent system.
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%.
According to some embodiments of the invention, the amino-enriched pitch hollow spheres have a diameter distribution of 1 to 1000 nm.
According to some embodiments of the invention, the nitrogen content of the amino-enriched pitch hollow spheres is 10% to 25%, such as 10.5%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 19.5%, 21%, 23% and any value in between.
According to some embodiments of the invention, the polycyclic aromatic hydrocarbon-containing asphalt is selected from one or more of petroleum asphalt, coal tar asphalt, and natural asphalt.
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 compound is selected from one or more of the organic polycyclic amine compounds of C4-C10.
According to some embodiments of the invention, the organic polycyclic amine compound is selected from one or more of hexamethylenetetramine, triethylenediamine, diethylenetriamine and cyclohexylamine.
According to some embodiments of the invention, the acidic organic solvent system comprises 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 polar solvents.
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.
According to some embodiments of the invention, the organic carboxylic acid is selected from one or more of the group consisting of C1-C6 organic carboxylic acids.
According to some embodiments of the invention, the organic carboxylic acid is selected from one or more of glacial acetic acid, propionic acid, glycolic acid, citric acid and formic acid.
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 polycyclic amine compound is 1 (0.5-5), preferably 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 1:1, 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), preferably 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), 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 mass of the polycyclic aromatic hydrocarbon and/or the polycyclic aromatic hydrocarbon-containing asphalt and the organic carboxylic acid is 1 (0.01-0.2).
In some preferred embodiments of the present invention, the polycyclic aromatic hydrocarbon and/or the polycyclic aromatic hydrocarbon-containing asphalt is 10 parts by mass, and the organic polycyclic amine compound is 0.1 to 50 parts by mass; 10-600 parts by mass of the organic solvent; preferably 100-300 parts by mass; the organic carboxylic acid is 0.01-5 parts by mass.
According to some embodiments of the present invention, the temperature of the reaction is 100-.
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. The N content in the amino-enriched asphalt is 10-25% by element analysis.
In some preferred embodiments of the present invention, the organic polycyclic amine compound is hexamethylenetetramine. The inventor creatively discovers that compared with the classical Duff reaction, the reaction conditions of the amino-enriched asphalt are more severe, the reaction temperature is higher, the HMTA is excessive, so that multiple substitution reactions can occur in the synthesis process, the substitution products and the polycondensation products thereof are various, and the complex mass spectrum structure of the amino-enriched asphalt in the application is caused, which is not reported in previous researches.
In order to achieve the second purpose, the invention firstly proposes the following technical scheme:
a preparation method of amino-enriched asphalt hollow spheres comprises the following steps:
s1: reacting polycyclic aromatic hydrocarbon and/or asphalt containing polycyclic aromatic hydrocarbon with an organic polycyclic amine compound in an acidic organic solvent system to obtain the amino-enriched asphalt;
s2: dissolving the amino-enriched asphalt obtained in the step S1 in a first solvent to obtain a precursor solution;
s3: and (4) carrying out spray drying on the precursor solution obtained in the step S2.
According to some embodiments of the invention, the polycyclic aromatic hydrocarbon-containing asphalt is selected from one or more of petroleum asphalt, coal tar asphalt, and natural asphalt.
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 compound is selected from one or more of the organic polycyclic amine compounds of C4-C10.
According to some embodiments of the invention, the organic polycyclic amine compound is selected from one or more of hexamethylenetetramine, triethylenediamine, diethylenetriamine and cyclohexylamine.
In some preferred embodiments of the present invention, the organic polycyclic amine compound is hexamethylenetetramine, and the inventors have creatively found that hexamethylenetetramine is very easy to protonate and is more likely to react with electron-rich polycyclic aromatic hydrocarbon to introduce amino groups.
According to some embodiments of the invention, the acidic organic solvent system comprises 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 polar solvents.
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.
According to some embodiments of the invention, the organic carboxylic acid is selected from one or more of the group consisting of C1-C6 organic carboxylic acids.
According to some embodiments of the invention, the organic carboxylic acid is selected from one or more of glacial acetic acid, propionic acid, glycolic acid, citric acid and formic acid.
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 polycyclic amine compound is 1 (0.5-5), preferably 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 1:1, 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), preferably 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), 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 mass ratio of the polycyclic aromatic hydrocarbon and/or the polycyclic aromatic hydrocarbon-containing asphalt to the organic carboxylic acid is 1 (0.01-0.2).
In some preferred embodiments of the present invention, the polycyclic aromatic hydrocarbon and/or the polycyclic aromatic hydrocarbon-containing asphalt is 10 parts by mass, and the organic polycyclic amine compound is 0.1 to 50 parts by mass; 10-600 parts by mass of the organic solvent; preferably 100-300 parts by mass; the organic carboxylic acid is 0.01-5 parts by mass.
According to some embodiments of the present invention, the temperature of the reaction is 100-.
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-.
According to some embodiments of the present invention, the spray drying in step S3 comprises the steps of:
a: introducing the precursor solution into an atomizer to form liquid drops;
b: and (4) carrying the liquid drops in the A into an evaporation chamber by using a carrier gas for evaporation.
According to some embodiments of the invention, the first solvent is a good solvent for the amino-enriched pitch.
According to some embodiments of the invention, the first solvent is selected from one or more of water, C1-C6 alcohols, C3-C6 ketones, tetrahydrofuran, and dimethylsulfoxide.
According to some embodiments of the invention, the first solvent is selected from one or more of water, ethanol, methanol, acetone, tetrahydrofuran, and dimethylsulfoxide.
According to some embodiments of the present invention, the mass ratio of the amino-enriched pitch to the first solvent is 1 (10-500), preferably 1 (50-300).
According to some embodiments of the present invention, other optimized means, such as mechanical, electrical, optical, magnetic, acoustic, and other auxiliary dispersing means, may be added in steps S1-S3, specifically, a mechanical stirrer, a magnetic stirrer, an ultrasonic disperser, an electromagnetic stirrer, and other devices having dispersing function are used in the process of forming the precursor solution and/or evaporating the solvent.
According to some embodiments of the invention, the precursor solution is introduced at a rate of 0.1-3ml/min, preferably 0.5-1 ml/min.
According to some embodiments of the invention, the oscillation frequency of the nebulizer is 1-3 MHz.
In some preferred embodiments of the invention, the vibrational frequency of the nebulizer is 1.7MHz or 2.4 MHz.
According to some embodiments of the invention, the power of the atomizer is 10W to 1000W.
According to some embodiments of the invention, the carrier gas is an inert gas, preferably nitrogen.
According to some embodiments of the invention, the carrier gas has a flow rate of 0.1L/min to 0.5L/min.
According to some embodiments of the invention, the temperature of the evaporation is between 350 ℃ and 700 ℃, preferably between 400 ℃ and 600 ℃.
The atomizer in the present invention is an atomizer conventionally used in spray drying, preferably an ultrasonic atomizer.
According to some embodiments of the invention, the spray drying of step S3 further comprises step C: the product was collected at the outlet, washed several times with washing liquid and subsequently dried.
According to some embodiments of the invention, the washing liquid comprises one or more of water, acetone and ethanol.
In some embodiments of the present invention, the spray drying process of step S3 comprises the following steps: and (3) introducing the precursor solution into an ultrasonic atomizer by using a peristaltic pump to be atomized into liquid drops, introducing the liquid drops into an evaporation chamber along with carrier gas, evaporating the solvent, converting the liquid drops into hollow spheres, and collecting the product at an outlet by using a filter membrane. Repeatedly washing with water, acetone and ethanol, and drying at 60 deg.C to obtain amino-enriched asphalt hollow spheres.
The inventors surprisingly found that the amino-enriched asphalt of the invention can be further prepared into hollow small-ball materials with uniform and regular shapes by the preparation method, thereby further improving the economic and application values of the amino-enriched asphalt.
In a third aspect of the present invention, there is provided the amino-enriched hollow asphalt beads of the first aspect or the amino-enriched hollow asphalt beads prepared by the method of the second aspect in CO2Application in selective adsorption separation.
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 hollow spheres prepared by the invention introduce high-content amino into asphalt materials. The nitrogen atoms contained in the amino groups are close to the carbon atoms in structure, so that the material structure can not be obviously distorted in the process of substituting the carbon atoms in the carbon skeleton as heteroatoms, and the structure of the carbon material can be further adjusted and the surface property of the material can be further changed, such as dislocation, bending, dislocation and the like with unpaired electronic defect sites generated on a graphite microcrystal plane layer 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 hollow spheres are nano-scale spherical materials, can be used as high-efficiency Oxygen Reduction Reaction (ORR) electrocatalysts, electrochemical capacitors, lithium ion batteries, adsorbents, catalyst carriers and the like by combining the characteristic of being rich in amino, and have high economic and application values.
(4) The amino-enriched asphalt hollow spheres can be processed simply to obtain the nitrogen-containing carbon material. Compared with pure carbon materials, the material has higher value and wider application in the fields of energy storage, hydrogen storage, catalysis and adsorption, oral drugs, blood purification, military protection, chromatographic columns and the like.
(5) The amino-enriched asphalt hollow globule is prepared by directly reacting polycyclic aromatic hydrocarbon with organic polycyclic amine compounds, and a modified high-nitrogen carbon product can be obtained after the polycyclic aromatic hydrocarbon and the organic polycyclic amine compounds are carbonized. 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 a Transmission (TEM) photograph of amino-enriched asphalt hollow spheres 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 intended to limit the present invention.
CO (carbon monoxide) of amino-enriched asphalt hollow spheres tested by utilizing double-component gas physical adsorption analyzer2/N2The selectivity coefficient of (a).
The content of C, H, N element in the sample was measured by using a CE440 full-automatic element analyzer manufactured by EAI of America.
Example 1
10g of coal tar pitch and 0.2mol of HMTA (28.04g) were dissolved in 300ml of methylpyrrolidone. 0.01mol of glacial acetic acid (0.60g) was slowly added dropwise thereto at 200 ℃ N2The reaction was stirred for 5 hours under the protection of atmosphere. After cooling to room temperature, the product was separated and purified using a 180 ℃ rotary vacuum evaporator. The obtained asphalt is further purified in a vacuum oven at 160 ℃ for 10 hours to obtain amino-enriched asphalt.
Weighing 1g of amino-enriched asphalt, dissolving in 150ml of ethanol solution, and performing ultrasonic treatment for 30min until the asphalt is completely dissolved to obtain a precursor solution. The precursor solution was introduced into an ultrasonic atomizer at 0.5ml/min by means of a peristaltic pump and atomized into droplets. The vibration frequency of the ultrasonic atomizer was set to 2.4MHz and the power was 100W. Using 0.5ml/min N2The droplets were carried to an evaporation chamber at 500 ℃ and the product was collected on a filter membrane at the outlet. And repeatedly washing with water, acetone and ethanol, and drying at 60 ℃ to obtain the amino-enriched asphalt hollow spheres.
The samples were observed using an EOL-2010 transmission electron microscope at 200kV accelerating voltage: and dispersing the prepared amino-enriched asphalt hollow spheres in ethanol, and dripping the amino-enriched asphalt hollow spheres on a copper net covered with a micro-grid after ultrasonic dispersion. The samples were observed with a JEOL-2010 transmission electron microscope at an accelerating voltage of 200 kV. The obtained amino-enriched asphalt hollow spheres are black, regular in shape and about 15-50 nm in particle size distribution.
To further explore the basic structure of the sample, infrared spectroscopy was performed, and fig. 2 shows the infrared spectrum of the amino-enriched asphalt in example 1. At 3423cm-1The compound shows a characteristic adsorption peak of an N-H group at 1607, 799-663 cm-1The peak at the position of the aromatic ring is 2931 to 2853cm-1Is represented by CH2Characteristic adsorption peak of the group at 2207cm-1And (C) shows a weak adsorption peak of the C ═ N group. Tests have shown that it successfully introduces amine-type components on hydrocarbons.
The sample of example 1 was observed using cross-polarization/magic angle spinning solid-state nuclear magnetic spectroscopy (CP/MAS 13C NMR), and the nuclear magnetic spectrum of the amino-enriched pitch of example 1 is shown in FIG. 3. The chemical shift C-N group of carbons was about 148 and 152ppm, the aromatic carbons were about 140, 134, 128 and 125ppm, and the alpha carbon of the methylene carbon linking the benzene ring and the amino group was about 49 ppm.
The nitrogen content of the amino-enriched asphalt hollow spheres tested by the elemental analysis method is 19.78%.
CO of amino-enriched asphalt hollow spheres2/N2The selectivity coefficient of (a) was 37.36. Compared with activated carbon CO2/N2Selectivity coefficient of 6, amino-enriched hollow spheres of asphalt show excellent CO2And (4) selectivity.
Example 2
10g of petroleum asphalt, 0.2mol of HMTA (28.04g) were dissolved in 300ml of methylpyrrolidone. Slowly adding 0.01mol (0.60g) of glacial acetic acid dropwise, and heating at 200 deg.C under N2The reaction was stirred for 5 hours under the protection of atmosphere. After cooling to room temperature, the product was separated and purified using a 180 ℃ rotary vacuum evaporator. The obtained asphalt is further purified in a vacuum oven at 160 ℃ for 10 hours to obtain amino-enriched asphalt.
Weighing 1g of amino-enriched asphalt, dissolving in 150ml of ethanol solution, and performing ultrasonic treatment for 30min until the asphalt is completely dissolved to obtain a precursor solution. The precursor solution was introduced into an ultrasonic atomizer at 0.5ml/min by means of a peristaltic pump and atomized into droplets. The vibration frequency of the ultrasonic atomizer was set to 2.4MHz and the power was 100W. Using 0.5ml/min N2The droplets were carried into an evaporation chamber at 500 ℃ and the product was collected on a filter membrane at the outlet. Repeatedly washing with water, acetone and ethanol, and drying at 60 deg.C to obtain amino-enriched asphalt hollow spheres.
The obtained amino-enriched asphalt hollow spheres are black, regular in shape and 20-70 nm in particle size distribution. In addition, infrared spectrum test is carried out on the product of the amino-enriched asphalt, tests show that amine components are successfully introduced into hydrocarbon, the nitrogen content in the amino-enriched asphalt hollow spheres is 16.81 percent according to an element method, and the CO content of the amino-enriched asphalt hollow spheres is tested by the element method2/N2Has a selectivity coefficient of 25.65.
Example 3
10g of coal tar pitch and 0.2mol of HMTA (28.04g) were dissolved in 300ml of methylpyrrolidone. 0.01mol of glacial acetic acid (0.60g) was slowly added dropwise thereto at 200 ℃ N2The reaction was stirred for 5 hours under the protection of atmosphere. After cooling to room temperature, the product was separated and purified using a 180 ℃ rotary vacuum evaporator. The obtained asphalt is further purified in a vacuum oven at 160 ℃ for 10 hours to obtain amino-enriched asphalt.
0.5g of amino-enriched asphalt is weighed and dissolved in 150ml of acetone solution, and ultrasonic treatment is carried out for 30min until the asphalt is completely dissolved, so as to obtain precursor solution. The precursor solution was introduced into an ultrasonic atomizer at 1ml/min by means of a peristaltic pump and atomized into droplets. The vibration frequency of the ultrasonic atomizer was set to 2.4MHz and the power was 100W. Using 0.5ml/min N2The droplets are brought into an evaporation chamber with a temperature of 600 ℃, and the product is collected by a filter membrane at an outlet. Repeatedly washing with water, acetone and ethanol, and drying at 60 deg.C to obtain amino-enriched asphalt hollow spheres.
The obtained amino-enriched asphalt hollow spheres are black, regular in shape and 50-100nm in particle size distribution. In addition, infrared spectrum test is carried out on the product of the amino-enriched asphalt, tests show that amine components are successfully introduced into hydrocarbon, the nitrogen content in the amino-enriched asphalt hollow spheres is 13.63 percent according to an element method, and CO of the amino-enriched asphalt hollow spheres is tested2/N2The selectivity coefficient of (3) was 19.89.
Example 4
10g of coal tar pitch and 0.2mol of HMTA (28.04g) were dissolved in 300ml of methylpyrrolidone. Slowly adding 0.01mol (0.60g) of glacial acetic acid dropwise, and heating at 200 deg.C under N2The reaction was stirred for 5 hours under the protection of atmosphere. After cooling to room temperature, the product was separated and purified using a 180 ℃ rotary vacuum evaporator. The obtained asphalt is further purified in a vacuum oven at 160 ℃ for 10 hours to obtain amino-enriched asphalt.
0.5g of amino-enriched asphalt is weighed and dissolved in 150ml of ethanol solution, and ultrasonic treatment is carried out for 30min until the asphalt is completely dissolved, so as to obtain precursor solution. The precursor solution was introduced into an ultrasonic atomizer at 1ml/min by means of a peristaltic pump and atomized into droplets. The vibration frequency of the ultrasonic atomizer was set to 2.4MHz and the power was 100W. Using 0.5ml/min N2The droplets were carried into an evaporation chamber at 700 ℃ and the product was collected on a filter membrane at the outlet. Repeatedly washing with water, acetone and ethanol, and drying at 60 deg.C to obtain amino-enriched asphalt hollow spheres.
The obtained amino-enriched asphalt hollow spheres are black, have regular shapes and have the particle size distribution of 50-100 nm. In addition, 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 amino-enriched asphalt hollow spheres is 11.20 percent and the CO content in the amino-enriched asphalt hollow spheres is tested by an element analysis method2/N2The selectivity coefficient of (a) was 11.28.
Example 5
10g of coal tar pitch and 0.2mol of HMTA (28.04g) were dissolved in 300ml of methylpyrrolidone. 0.01mol (0.74g) of propionic acid was slowly added dropwise thereto, and the mixture was heated at 200 ℃ under nitrogen2The reaction was stirred for 5 hours under the protection of atmosphere. After cooling to room temperature, the product was separated and purified using a 180 ℃ rotary vacuum evaporator. The obtained asphalt is further purified in a vacuum oven at 160 ℃ for 10 hours to obtain amino-enriched asphalt.
Weighing 1g of amino-enriched asphalt, dissolving in 150ml of aqueous solution, and carrying out ultrasonic treatment for 30min until the asphalt is completely dissolved to obtain a precursor solution. The precursor solution was introduced into an ultrasonic atomizer at 1ml/min by means of a peristaltic pump and atomized into droplets. The vibration frequency of the ultrasonic atomizer was set to 2.4MHz and the power was 100W. Using 0.5ml/min N2Mixing liquidDropping into an evaporation chamber with the temperature of 500 ℃, and collecting the product at an outlet through a filter membrane. Repeatedly washing with water, acetone and ethanol, and drying at 60 deg.C to obtain amino-enriched asphalt hollow spheres.
The obtained amino-enriched asphalt hollow spheres are black, have regular shapes, and have the particle size distribution of 100-300 nm. 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 amino-enriched asphalt hollow spheres obtained by element method tests is 23.42%.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not set any limit to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims (10)

1. The amino-enriched asphalt hollow bead is prepared by carrying out spray drying on amino-enriched asphalt, wherein the amino-enriched asphalt comprises polycyclic aromatic hydrocarbons and/or a product of reaction of the asphalt containing the polycyclic aromatic hydrocarbons and organic polycyclic amine compounds in an acidic organic solvent system.
2. Amino-enriched bitumen hollow spheres according to claim 1, wherein the diameter distribution of the amino-enriched bitumen hollow spheres is between 1 and 1000nm and/or the nitrogen content of the amino-enriched bitumen hollow spheres is between 10% and 25%.
3. A preparation method of amino-enriched asphalt hollow spheres comprises the following steps:
s1: reacting polycyclic aromatic hydrocarbon and/or asphalt containing polycyclic aromatic hydrocarbon with an organic polycyclic amine compound in an acidic organic solvent system to obtain the amino-enriched asphalt;
s2: dissolving the amino-enriched asphalt obtained in the step S1 in a first solvent to obtain a precursor solution;
s3: and (4) carrying out spray drying on the precursor solution obtained in the step S2.
4. The amino-enriched asphalt hollow pellet or the method as claimed in any one of claims 1 to 3, wherein the polycyclic aromatic hydrocarbon-containing asphalt is selected from one or more of petroleum asphalt, coal tar asphalt and natural asphalt;
and/or 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.
5. The amino-enriched bituminous hollow pellet or method of any one of claims 1-4, 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, propionic acid, glycolic acid, citric acid and formic acid.
6. The amino-enriched hollow asphalt pellet or the method as claimed in any one of claims 1 to 5, wherein 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), preferably 1 (0.5-3);
and/or 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 (0.01-0.2);
and/or the temperature of the reaction is 100-250 ℃, preferably 150-200 ℃, preferably the reaction is carried out under an inert atmosphere.
7. The amino-enriched bituminous hollow pellet or method according to any one of claims 1-6, characterized in that the spray drying comprises the steps of:
a: introducing the precursor solution into an atomizer to form liquid drops;
b: and (4) carrying the liquid drops in the A into an evaporation chamber by using a carrier gas for evaporation.
8. The amino-enriched pitch hollow sphere or method according to any one of claims 1 to 7, wherein the first solvent is a good solvent for the amino-enriched pitch, preferably the first solvent is selected from one or more of water, C1-C6 alcohol, C3-C6 ketone, tetrahydrofuran and dimethylsulfoxide, more preferably from one or more of water, ethanol, methanol, acetone, tetrahydrofuran and dimethylsulfoxide;
and/or the mass ratio of the amino-enriched asphalt to the first solvent is 1 (10-500), preferably 1 (50-300).
9. Amino-enriched pitch hollow spheres or process according to any of claims 1 to 8, wherein the precursor solution is introduced at a rate of 0.1 to 3ml/min, preferably 0.5 to 1 ml/min;
and/or the vibration frequency of the atomizer is 1-3MHz, and the power is 10W-1000W;
and/or the carrier gas is inert gas, preferably nitrogen, and the flow rate of the carrier gas is 0.1L/min-0.5L/min;
and/or the temperature of the evaporation is 350 ℃ to 700 ℃, preferably 400 ℃ to 600 ℃.
10. Amino-enriched bitumen hollow spheres according to any of claims 1 to 9 or prepared by a method according to any of claims 3 to 9 in CO2Application in the field of selective adsorption separation.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4431513A (en) * 1982-03-30 1984-02-14 Union Carbide Corporation Methods for producing mesophase pitch and binder pitch
CN101259961A (en) * 2008-04-10 2008-09-10 华东理工大学 Method for preparing nitrogen-containing asphalt-base spherical activated carbon
CN104388109A (en) * 2014-12-11 2015-03-04 厦门大学 Preparation method of soluble intermediate phase asphalt
CN110157459A (en) * 2019-05-15 2019-08-23 国家能源投资集团有限责任公司 The preparation method of mesophase pitch bead

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4431513A (en) * 1982-03-30 1984-02-14 Union Carbide Corporation Methods for producing mesophase pitch and binder pitch
CN101259961A (en) * 2008-04-10 2008-09-10 华东理工大学 Method for preparing nitrogen-containing asphalt-base spherical activated carbon
CN104388109A (en) * 2014-12-11 2015-03-04 厦门大学 Preparation method of soluble intermediate phase asphalt
CN110157459A (en) * 2019-05-15 2019-08-23 国家能源投资集团有限责任公司 The preparation method of mesophase pitch bead

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