CN111825796A - For CO2Adsorbed polyacrylate composite material and preparation method thereof - Google Patents

For CO2Adsorbed polyacrylate composite material and preparation method thereof Download PDF

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CN111825796A
CN111825796A CN202010755732.7A CN202010755732A CN111825796A CN 111825796 A CN111825796 A CN 111825796A CN 202010755732 A CN202010755732 A CN 202010755732A CN 111825796 A CN111825796 A CN 111825796A
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polyacrylate
emulsion
composite material
amine
tetraethylenepentamine
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CN111825796B (en
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叶坚强
郭素丽
刘海林
黄显琴
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Wuhan Huicarbon Technology Co ltd
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Abstract

The invention discloses a method for preparing CO2The adsorbed polyacrylate composite material is prepared by amination grafting of porous polyacrylate and surface end capping of epoxy resin2An adsorbed polyacrylate composite. The invention has the following advantages: the synthesis process is simple and the price is low; three-level interconnected through hole structure for CO2The rapid adsorption/desorption needs, the blockage of the pore passage caused by the water vapor in the flue gas can not be caused, the particle size distribution is uniform, the size of the ball is controllable, and the requirement of the fluidized bed can be better met.

Description

For CO2Adsorbed polyacrylate composite material and preparation method thereof
Technical Field
The invention relates to a method for CO2An adsorbed polyacrylate composite material and a preparation method thereof, belonging to CO2The field of separation.
Background
As is well known, CO2Emissions are one of the important causes of climate warming. Worldwide annual combustion of fossil fuels to produce CO2About 35.5Gt, while the carbon fixation of green plants is less than 6%, this severe imbalance between artificial emissions and natural consumption results in atmospheric CO2The concentration increases sharply. China's annual CO2The emission is about 10Gt, and the energy structure mainly based on fossil energy does not change in the near future. Developing large scale CO2Trapping and utilization are attracting more and more extensive attention. In various CO2In the separation method, the alcohol amine solution absorption method has high separation efficiency, wide application range and high product purity, is a relatively mature technology, but has the problems of high separation energy consumption, easy volatilization and degradation of organic amine, serious corrosion of equipment and the like. In contrast, the solid adsorption separation has low energy consumption, simple process and no equipment corrosion, and has become CO2One important development of trapping technology.
However, the existing solid amine adsorbing materials have the problem of serious insufficient stability. This is because the organic amine carried in the material is easily dissolved, volatilized, leaked, oxidized, and removes CO at high temperature2Urea and cyclic ureas are also produced, leading to permanent deactivation. In addition, the existing solid amine adsorption material usually adopts mesoporous silicon as a matrix, and a pore channel is very easy to smokeThe water vapor in the gas is blocked, so that the CO is separated in the adsorption mode2Previously, the flue gas had to be dehydrated, resulting in a substantial increase in both energy consumption and investment costs.
CN102516435A discloses a method for preparing porous polymer by high internal phase emulsion polymerization, and CN102731704A discloses a method for preparing porous polymer particles by a miniemulsion template method, wherein the materials prepared by the two methods are both blocky and are not suitable for a fluidized bed, and the pore size distribution is disordered and larger.
In the preparation and performance of the poly (acryloyl diethylenetriamine) carbon dioxide adsorption resin (polymer material science and engineering, 2012, 28(11):145-148), methyl acrylate and divinylbenzene are adopted for suspension copolymerization, and then the suspension copolymerization is reacted with diethylenetriamine to obtain the macroporous crosslinked poly (acryloyl diethylenetriamine) (PAM) adsorption resin.
Most of the conventional concentrated emulsion polymerization materials are bulk materials suitable for a fixed bed operation process, but the organic porous materials are limited by low heat transfer efficiency, so that large-scale industrialization is difficult to realize. The fluidized bed process has better mass transfer and heat transfer efficiency, so that the problem of low inherent heat transfer efficiency of the organic polymer can be completely solved, the fluidized bed process can more easily realize continuous operation of adsorption/desorption circulation, and the adsorption/desorption dynamics can be greatly improved. Therefore, the invention creatively combines emulsion polymerization and suspension polymerization to prepare the spherical polymer material with uniform intercommunicated macroporous structure, thereby being suitable for the fluidized bed process.
Disclosure of Invention
In view of the above problems, it is an object of the present invention to provide a method for treating CO2The adsorption separation of the polyacrylate composite material is more effective.
It is another object of the present invention to provide a CO which can be suitably used in a fluidized bed2Adsorbing and separating the polyacrylate composite material.
Another purpose of the invention is to provide CO with a three-level interconnection macroporous structure2Adsorbing and separating the polyacrylate composite material.
Another purpose of the invention is to improve the hydrophobic property of the material and CO with the properties of compression resistance, abrasion resistance and heat resistance2Adsorbing and separating the polyacrylate composite material.
In order to achieve the purpose, the invention adopts the following technical scheme:
for CO2The adsorbed polyacrylate composite material is prepared by amination grafting of porous polyacrylate and surface end capping of epoxy resin2An adsorbed polyacrylate composite.
The porous polyacrylate is polyacrylate spheres formed by crosslinking three monomers, namely methyl methacrylate, n-butyl acrylate and glycidyl methacrylate.
The amination grafting adopts a mixed solution of an amino modifier and one of glycidyl methacrylate, epichlorohydrin and epoxybutane. The preferable range of the dosage ratio (mass ratio) of the amine modifier to the glycidyl methacrylate, the epichlorohydrin and the epoxybutane is (0.5-2): 1.
the amino modifier is one or more of diethanolamine, ethylenediamine, diethylenetriamine, tetraethylenepentamine, pentaethylenehexamine, tetraethylenepentamine acrylonitrile, melamine, urea and polyethyleneimine.
A preparation method of a polyacrylate composite material comprises the following steps:
(1) preparing an acrylic ester monomer, a cross-linking agent, a surfactant, a pore-forming agent, an initiator and water into emulsion;
(2) preparing a dispersion phase from water and a dispersing agent;
(3) adding the emulsion obtained in the step (1) into the dispersed phase obtained in the step (2), dispersing the emulsion into balls at a certain rotating speed, adding a reducing agent after the emulsion is stabilized, and separating and drying the mixture after the emulsion is solidified to prepare spherical porous polyacrylate balls;
(4) and (4) soaking the porous polyacrylate balls obtained in the step (3) in a solution containing an amino modifier, heating for amination grafting modification, and then carrying out surface end-capping treatment with epoxy resin to obtain the polyacrylate composite material.
The polyacrylate monomer is methyl methacrylate, n-butyl acrylate and glycidyl methacrylate; the cross-linking agent is an acrylate cross-linking agent.
The solution containing the amino modifier is a mixed solution of the amino modifier and one of glycidyl methacrylate, epichlorohydrin and epoxybutane.
The heating temperature of the step (4) is 60-80 ℃.
The amino modifier is one or more of diethanolamine, ethylenediamine, diethylenetriamine, tetraethylenepentamine, pentaethylenehexamine, tetraethylenepentamine acrylonitrile, melamine, urea and polyethyleneimine.
The cross-linking agent in the step (1) is trimethylolpropane triacrylate, the surfactant is a polyoxypropylene polyoxyethylene copolymer, the initiator is benzoyl peroxide, and the pore-forming agent is toluene; the reducing agent in the step (3) is N, N, N ', N' -tetramethylethylenediamine.
The invention adopts three monomers of methyl methacrylate, n-butyl acrylate and glycidyl methacrylate as raw materials of polyacrylate, and has the following technical effects: by regulating the ratio of the monomer to the cross-linking agent and the volume ratio of the water phase to the oil phase, base materials with different hardness and elasticity can be obtained, so that the material is suitable for different environments. The polymerization reaction speed and the polymerization degree can be greatly accelerated by adopting the ratio of the common polymerization of the three specific monomers to the single monomer, so that the polymerization can be completed within 20min, and the mass industrial production of materials is facilitated; and the three specific monomers can enable the internal pore structure of the obtained material to be uniform and ordered, so that the utilization rate of the amino group of the material is favorably improved, and the carbon dioxide adsorption and separation capacity of the material is improved. The specific content ratio of the three monomers can be regulated according to actual needs, and the preferable ratio range of the mass percentage content of the three monomers of methyl methacrylate, n-butyl acrylate and glycidyl methacrylate is (10% -30%): (10% -30%): (60% -80%).
The invention adopts the epoxy resin for surface end-capping treatment, the epoxy resin can further react with the cross-linked amine on the surface of the obtained polyacrylate sphere to obtain a solid product, the surface aperture can be reduced, and simultaneously the compression resistance, heat resistance, wear resistance and other properties of the material are enhanced, so that the obtained product is more suitable for the use of a fluidized bed. Epoxy groups in the epoxy resin can react with organic amine on the surface layer of the material, so that the epoxy groups are attached to the surface of the material to form a protective shell, the developed surface hole part of the material is closed, the carbon dioxide trapping capacity of the material is slightly reduced, the organic amine in the material can be effectively prevented from leaking, and the stability of the material is greatly improved; and the epoxy resin is a hydrophobic material, and the formed protective shell can prevent moisture from contacting with organic amine, so that the influence of the moisture on the adsorption process can be avoided.
The invention selects glycidyl methacrylate and the like as modifiers, can perform crosslinking reaction with tetraethylenepentamine, can obviously improve the stability of amine, and prevents the dissolution, volatilization, oxidation and carbamidation of the amine, so that the amino functional polyacrylate composite material has good stability. This is because primary amine and secondary amine are present in tetraethylenepentamine, and although other primary amines have strong carbon dioxide adsorption ability, primary amine can react with carbon dioxide at high temperature to produce urea or the like, thereby losing the adsorption ability of the material, while epoxy groups in modifiers such as glycidyl methacrylate can react with primary amine to produce secondary amine, which is slightly reduced in adsorption ability but remarkably improved in stability.
Unlike common emulsion polymerization, the present invention adopts emulsion suspension polymerization, which includes preparing concentrated emulsion, adding the emulsion to the third phase comprising water and dispersant via stirring to disperse the emulsion into small droplets, and polymerizing to obtain spherical porous material. The novel composite material prepared by the invention is particularly suitable for a fluidized bed, and the adsorption material has the following components: 1. the material synthesis process is simple and the price is low; 2. the material is of a three-level interconnected through hole structure and meets the requirement of CO2Rapid adsorption/desorption requirements ofAfter amino functionalization treatment, excellent thermodynamic and kinetic properties are shown; 3. due to the special macroporous structure, the blockage of the pore channel by the water vapor in the flue gas can not be caused; 4. the material is inert to equipment, so that the equipment is not corroded; 5. the material has uniform particle size distribution and controllable particle size, so that the material preparation process is closer to industrial application; 6. the spherical material has good elasticity and wear resistance, and meets the requirements of a fluidized bed process.
Drawings
FIG. 1 is a schematic representation of a polyacrylate entity; as can be seen from FIG. 1, the obtained polyacrylate is in the form of uniform spherical particles and can be directly used as a fluidized bed adsorption material;
FIG. 2 is a cross-sectional scanning electron micrograph of the composite; as can be seen from FIG. 2, the material has a uniform, ordered and highly connected internal pore structure, and the pore diameter is intensively distributed in the range of 1-5 μm;
FIG. 3 is a scanning electron microscope image of the surface of the material before the epoxy resin surface modification; as can be seen from fig. 3, the material has a developed surface pore structure, which is beneficial to improve the adsorption capacity of the material, but also causes organic amine inside the material to easily leak, thereby affecting the stability of the material;
FIG. 4 is a scanning electron microscope image of the surface of the material after the epoxy resin surface modification; as can be seen from FIG. 4, the number and diameter of the pores on the surface of the material are greatly reduced after the epoxy resin is terminated, which is beneficial to improving the stability of the material.
Detailed Description
The present invention will be described in detail with reference to examples
Example 1
(1) Putting 0.4g of methyl methacrylate, 0.4g of tert-butyl methacrylate, 0.7g of glycidyl methacrylate and 1g of trimethylolpropane triacrylate into a flask, adding 3ml of toluene and 0.3g of polyoxypropylene polyoxyethylene copolymer, dropwise adding 10ml of deionized water into the flask at the rotating speed of 1000r/min, continuously stirring for 10min after dropwise adding is finished to obtain stable emulsion, taking out the emulsion, adding 0.1g of benzoyl peroxide, and stirring at a high speed of 5000r/min for 2 min;
(2) adding 0.3g of polyvinyl alcohol into 150ml of deionized water to prepare a dispersion phase, adding the emulsion into the dispersion phase, dispersing the emulsion into balls at a stirring speed of 250r/min, adding 6 drops of N, N, N ', N' -tetramethylethylenediamine serving as a reducing agent after the emulsion is stabilized, taking out the balls after solidification, and drying the balls in an oven at 70 ℃ for 2 hours to obtain spherical particles with the particle size of 0.3-1.0 mm;
(3) taking 2.5g of spherical particles, and putting 10ml of mixed solution of glycidyl methacrylate and tetraethylenepentamine, wherein the mass ratio of the glycidyl methacrylate to the tetraethylenepentamine is 1: 1.5; heating to 80 ℃, reacting for 20min, cooling at room temperature, adding 3ml of 5% epoxy resin methanol solution, and drying in a 70 ℃ oven for 2h to obtain the amino functional polyacrylate composite material.
Example 2
(1) Putting 0.2g of methyl methacrylate, 0.4g of tert-butyl methacrylate, 0.9g of glycidyl methacrylate and 1g of trimethylolpropane triacrylate into a flask, adding 3ml of toluene and 0.3g of polyoxypropylene polyoxyethylene copolymer, dropwise adding 10ml of deionized water into the flask at the rotating speed of 1000r/min, continuously stirring for 10min after dropwise adding is finished to obtain stable emulsion, taking out the emulsion, adding 0.1g of benzoyl peroxide, and stirring at a high speed of 5000r/min for 2 min;
(2) adding 0.3g of polyvinyl alcohol into 150ml of deionized water to prepare a dispersion phase, adding the emulsion into the dispersion phase, dispersing the emulsion into balls at a stirring speed of 250r/min, adding 6 drops of N, N, N ', N' -tetramethylethylenediamine serving as a reducing agent after the emulsion is stabilized, taking out the balls after solidification, and drying the balls in an oven at 70 ℃ for 2 hours to obtain spherical particles with the particle size of 0.3-1.0 mm;
(3) taking 2.5g of spherical particles, and putting 10ml of mixed solution of glycidyl methacrylate and tetraethylenepentamine, wherein the mass ratio of the glycidyl methacrylate to the tetraethylenepentamine is 1: 1; heating to 80 ℃, reacting for 20min, cooling at room temperature, adding 3ml of 5% epoxy resin methanol solution, and drying in a 70 ℃ oven for 2h to obtain the amino functional polyacrylate composite material.
Example 3
(1) Putting 0.4g of methyl methacrylate, 0.2g of tert-butyl methacrylate, 0.9g of glycidyl methacrylate and 1g of trimethylolpropane triacrylate into a flask, adding 3ml of toluene and 0.3g of polyoxypropylene polyoxyethylene copolymer, dropwise adding 10ml of deionized water into the flask at the rotating speed of 1000r/min, continuously stirring for 10min after dropwise adding is finished to obtain stable emulsion, taking out the emulsion, adding 0.1g of benzoyl peroxide, and stirring at a high speed of 5000r/min for 2 min;
(2) adding 0.3g of polyvinyl alcohol into 150ml of deionized water to prepare a dispersion phase, adding the emulsion into the dispersion phase, dispersing the emulsion into balls at a stirring speed of 250r/min, adding 6 drops of N, N, N ', N' -tetramethylethylenediamine serving as a reducing agent after the emulsion is stabilized, taking out the balls after solidification, and drying the balls in an oven at 70 ℃ for 2 hours to obtain spherical particles with the particle size of 0.3-1.0 mm;
(3) taking 2.5g of spherical particles, and putting 10ml of mixed solution of glycidyl methacrylate and tetraethylenepentamine, wherein the mass ratio of the glycidyl methacrylate to the tetraethylenepentamine is 1: 1.5; heating to 80 ℃, reacting for 20min, cooling at room temperature, adding 3ml of 5% epoxy resin methanol solution, and drying in a 70 ℃ oven for 2h to obtain the amino functional polyacrylate composite material.
Example 4
(1) Putting 0.4g of methyl methacrylate, 0.2g of tert-butyl methacrylate, 0.9g of glycidyl methacrylate and 1g of trimethylolpropane triacrylate into a flask, adding 3ml of toluene and 0.3g of polyoxypropylene polyoxyethylene copolymer, dropwise adding 10ml of deionized water into the flask at the rotating speed of 1000r/min, continuously stirring for 10min after dropwise adding is finished to obtain stable emulsion, taking out the emulsion, adding 0.1g of benzoyl peroxide, and stirring at a high speed of 5000r/min for 2 min;
(2) adding 0.3g of polyvinyl alcohol into 150ml of deionized water to prepare a dispersion phase, adding the emulsion into the dispersion phase, dispersing the emulsion into balls at a stirring speed of 250r/min, adding 6 drops of N, N, N ', N' -tetramethylethylenediamine serving as a reducing agent after the emulsion is stabilized, taking out the balls after solidification, and drying the balls in an oven at 70 ℃ for 2 hours to obtain spherical particles with the particle size of 0.3-1.0 mm;
(3) taking 2.5g of spherical particles, and putting 10ml of a mixed solution of epichlorohydrin and tetraethylenepentamine, wherein the mass ratio of the epichlorohydrin to the tetraethylenepentamine is 1: 1.5; heating to 80 ℃, reacting for 20min, cooling at room temperature, adding 3ml of 3% epoxy resin methanol solution, and drying in a 70 ℃ oven for 2h to obtain the amino functional polyacrylate composite material.
Comparative example 1: the procedure of example 1 was followed, omitting only the addition of glycidyl methacrylate.
Comparative example 2: the procedure of example 1 was used, omitting the glycidyl methacrylate and epoxy end-capping treatment steps.
Comparative example 3: the procedure of example 1 was used, omitting the epoxy capping treatment.
The performance test experimental data are as follows:
Figure BDA0002611504530000071

Claims (10)

1. for CO2The adsorbed polyacrylate composite material is characterized in that porous polyacrylate is subjected to amination grafting and then epoxy resin surface end capping treatment to obtain the material for CO2An adsorbed polyacrylate composite.
2. The polyacrylate composite according to claim 1, wherein the porous polyacrylate is polyacrylate beads crosslinked with three monomers of methyl methacrylate, n-butyl acrylate and glycidyl methacrylate.
3. The polyacrylate composite of claim 1 or 2 wherein said aminated graft is prepared by mixing an amine modifier with one of glycidyl methacrylate, epichlorohydrin and butylene oxide.
4. The polyacrylate composite material according to claim 3, wherein the amine modifier is one or more selected from diethanolamine, ethylenediamine, diethylenetriamine, tetraethylenepentamine, pentaethylenehexamine, tetraethylenepentamine acrylonitrile, melamine, urea, and polyethyleneimine.
5. A method for preparing the polyacrylate composite material according to claim 1, comprising the steps of:
(1) preparing an acrylic ester monomer, a cross-linking agent, a surfactant, a pore-forming agent, an initiator and water into emulsion;
(2) preparing a dispersion phase from water and a dispersing agent;
(3) adding the emulsion obtained in the step (1) into the dispersed phase obtained in the step (2), dispersing the emulsion into balls at a certain rotating speed, adding a reducing agent after the emulsion is stabilized, and separating and drying the mixture after the emulsion is solidified to prepare spherical porous polyacrylate balls;
(4) and (4) soaking the porous polyacrylate balls obtained in the step (3) in a solution containing an amino modifier, heating for amination grafting modification, and then carrying out surface end-capping treatment with epoxy resin to obtain the polyacrylate composite material.
6. The method of claim 5, wherein the polyacrylate monomer is methyl methacrylate, n-butyl acrylate and glycidyl methacrylate; the cross-linking agent is an acrylate cross-linking agent.
7. The method according to claim 5 or 6, wherein the solution containing the amine-based modifier is a mixed solution of the amine-based modifier and one of glycidyl methacrylate, epichlorohydrin and butylene oxide.
8. The production method according to any one of claims 5 to 7, wherein the heating temperature in the step (4) is 60 to 80 ℃.
9. The method according to any one of claims 5 to 8, wherein the amine modifier is one or more of diethanolamine, ethylenediamine, diethylenetriamine, tetraethylenepentamine, pentaethylenehexamine, tetraethylenepentamine acrylonitrile, melamine, urea, and polyethyleneimine.
10. The method according to any one of claims 5 to 9, wherein the cross-linking agent in step (1) is trimethylolpropane triacrylate, the surfactant is polyoxypropylene polyoxyethylene copolymer, the initiator is benzoyl peroxide, and the pore-forming agent is toluene; the reducing agent in the step (3) is N, N, N ', N' -tetramethylethylenediamine.
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