CN112547008A - Carbon microsphere for adsorbing dioxin - Google Patents

Carbon microsphere for adsorbing dioxin Download PDF

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CN112547008A
CN112547008A CN202011267645.3A CN202011267645A CN112547008A CN 112547008 A CN112547008 A CN 112547008A CN 202011267645 A CN202011267645 A CN 202011267645A CN 112547008 A CN112547008 A CN 112547008A
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carbon
dioxin
formaldehyde
carbon microsphere
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李顺
陈善良
刘勇
张永平
张双猛
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Guangdong Yina New Material Technology Co ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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    • B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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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
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract

The invention discloses a carbon microsphere for adsorbing dioxin, which is mainly prepared from the following raw materials in parts by weight: 25-35 parts of phenol, 25-40 parts of formaldehyde, 0.4-2 parts of an initiator, 30-50 parts of water, 1-10 parts of polyvinyl alcohol and 2-5 parts of a cross-linking agent; the sum of the parts by weight of the phenol, the formaldehyde, the initiator, the water, the polyvinyl alcohol and the cross-linking agent is 100 parts; the preparation method comprises the following steps: firstly, reacting phenol, formaldehyde, an initiator, water and polyvinyl alcohol to obtain a prepolymer, then adding a cross-linking agent, curing to obtain polymer microspheres, finally carbonizing in an inert atmosphere, and activating in a carbon dioxide atmosphere to obtain finished carbon microspheres. By implementing the method, the carbon microspheres with uniform particle size and large surface area can be obtained, and the adsorption rate of the carbon microspheres on dioxin is up to more than 80 percent and is more than 20 percent higher than that of the existing porous carbon material.

Description

Carbon microsphere for adsorbing dioxin
Technical Field
The invention relates to the technical field of dioxin adsorption, in particular to carbon microspheres for dioxin adsorption.
Background
Dioxins are a generic term for polychlorinated biphenyldioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), and are considered as "one of the most toxic poisons on the earth". Dioxin is fat soluble, can be enriched in human body, and can cause cancer and teratogenesis after long-term micro-intake. The main source of dioxin is currently waste incineration. Dioxin in the waste incineration flue gas exists in two forms of solid phase and gas phase. The solid-phase dioxin means that the dioxin exists in a solid phase after being adhered to other particles such as fly ash and the like and can be directly removed by a bag-type dust collector. While dioxin in the gas phase exists in the gas phase, which is difficult to be adsorbed. Research shows that 50-70% of dioxin exists in a solid phase form, and the solid phase dioxin is easy to adsorb and detect; conventional porous materials have poor adsorption of gas phase dioxin, which makes it difficult to detect and remove. An improved method is to use carbon nano tube to adsorb and detect, the carbon nano tube can form pi-pi combined bond with dioxin molecule, and the absorption of solid phase and gas phase dioxin is enhanced. However, the adsorption rate of dioxin is still difficult to meet the requirement, and the preparation cost of carbon nanotubes is too high to be popularized.
On the other hand, mesoporous carbon has attracted a wide range of attention because it has a rich pore structure and pore volume and is very expected to be used as an adsorbent, a catalyst support, an energy storage material, and the like. Compared with other mesoporous materials, the mesoporous carbon material has more special properties, such as higher specific surface area and porosity, structural plasticity, diversity of mesoporous shapes, adjustability of pore wall composition and properties and the like. In addition, the mesoporous carbon also has the advantages of simple synthesis, easy operation, no physiological toxicity and the like. Has great application prospect in the fields of electrochemical electrode materials, catalyst carriers, chromatographic column adsorbents, protein separation and the like. At present, the preparation of the mesoporous carbon microsphere mainly adopts a hard template and a soft template, the preparation process is relatively complex, the template is selective, and the precise regulation and control of the specific surface area of the mesoporous carbon microsphere are difficult to realize.
Disclosure of Invention
The invention aims to solve the technical problem of providing a carbon microsphere for adsorbing dioxin, which has uniform particle size and large surface area, and the adsorption rate of the carbon microsphere for adsorbing dioxin is up to more than 80%.
In order to solve the technical problems, the invention provides a carbon microsphere for adsorbing dioxin, which is mainly prepared from the following raw materials in parts by weight:
25-35 parts of phenol, 25-40 parts of formaldehyde, 0.4-2 parts of an initiator, 30-50 parts of water, 1-10 parts of polyvinyl alcohol and 2-5 parts of a cross-linking agent;
the sum of the parts by weight of the phenol, the formaldehyde, the initiator, the water, the polyvinyl alcohol and the cross-linking agent is 100 parts;
the preparation method comprises the following steps:
(1) uniformly mixing phenol, formaldehyde, an initiator and water, adding polyvinyl alcohol, and reacting at 90-100 ℃ for 0.5-2 h to obtain a prepolymer;
(2) adding a cross-linking agent into the prepolymer, reacting at 90-100 ℃ for 1-6 h, and curing to obtain polymer microspheres;
(3) carbonizing the polymer microspheres in an inert atmosphere, and then activating in a carbon dioxide atmosphere to obtain the finished carbon microspheres.
As an improvement of the above technical scheme, the weight ratio of phenol to formaldehyde is 1: (1-1.1).
As an improvement of the technical scheme, the initiator is one or more of diethylamine, triethylamine, triethanolamine, sodium carbonate and sodium hydroxide;
as an improvement of the technical scheme, the cross-linking agent is selected from one or more of diethylenetriamine, triethylenetetramine, hexamethylenetetramine and hexamethylphosphoric triamide.
As an improvement of the technical scheme, the initiator is triethylamine, and the cross-linking agent is diethylenetriamine.
As an improvement of the technical scheme, the health-care food is prepared from the following raw materials in parts by weight:
26-30 parts of phenol, 26-35 parts of formaldehyde, 0.7-1.0 part of triethylamine, 33-38 parts of water, 2-6 parts of polyvinyl alcohol and 3-4 parts of diethylenetriamine;
the total weight of phenol, formaldehyde, triethylamine, water, polyvinyl alcohol and diethylenetriamine is 100 parts;
as an improvement of the technical scheme, in the step (3), the polymer microspheres are carbonized in an argon or nitrogen atmosphere, the carbonization temperature is 750-950 ℃, the carbonization time is 1-5 h, and the heating rate in the carbonization process is 5-10 ℃/min.
As an improvement of the technical scheme, in the step (3), the activation temperature is 750-950 ℃, and the activation time is 0.5-6 h.
As an improvement of the technical scheme, the purity of the nitrogen, the argon and the carbon dioxide is 99.9 to 99.999 percent.
As an improvement of the technical scheme, the particle size of the carbon microsphere is 1-200 mu m, and the specific surface area is 450-2500 m2A pore diameter of 1 to 15nm and a pore volume of 0.5 to 5cm3/g。
The implementation of the invention has the following beneficial effects:
the carbon microsphere is prepared from phenol, formaldehyde, an initiator, water, polyvinyl alcohol and a cross-linking agent; the polyvinyl alcohol can stabilize the cross-linking polymerization process of phenol and formaldehyde, thereby effectively regulating and controlling the particle size, specific surface area, pore volume and pore diameter of the carbon microsphere. Meanwhile, the carbon microsphere is subjected to high-temperature carbonization and then is activated in a carbon dioxide atmosphere, so that the particle size, the specific surface area, the pore volume and the pore diameter of the carbon microsphere can be further optimized. The carbon microsphere obtained based on the formula and the preparation method has the dioxin adsorption rate of over 80 percent.
Drawings
FIG. 1 is a flow chart of a method for preparing carbon microspheres for dioxin adsorption according to the present invention;
FIG. 2 is a microscopic topography of the carbon microsphere of example 1 of the present invention;
FIG. 3 is another topographical view of a carbon microsphere according to example 1 of the present invention;
FIG. 4 is a graph showing the adsorption profile of the carbon microspheres of example 1 of the present invention;
FIG. 5 is a graph showing the pore size distribution of the carbon microsphere of example 1;
FIG. 6 is a graph showing the results of an adsorption experiment of carbon microspheres in test example 1 of the present invention;
FIG. 7 is a graph showing the results of an adsorption experiment of carbon nanotubes in comparative test example 1 of the present invention;
FIG. 8 is a graph showing the results of an adsorption experiment of activated carbon in comparative test example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
The invention provides a carbon microsphere for adsorbing dioxin, which is mainly prepared from the following raw materials in parts by weight:
25-35 parts of phenol, 25-40 parts of formaldehyde, 0.4-2 parts of an initiator, 30-50 parts of water, 1-10 parts of polyvinyl alcohol and 2-5 parts of a cross-linking agent; the sum of the parts by weight of the phenol, the formaldehyde, the initiator, the water, the polyvinyl alcohol and the cross-linking agent is 100 parts.
Wherein, phenol and formaldehyde are main polymerization monomers, which can be condensed to form spherical phenolic resin, thereby providing a good foundation for preparing the carbon microspheres by later carbonization. Specifically, the phenol is used in an amount of 25 to 35 parts, preferably 26 to 30 parts, and illustratively 26 parts, 27 parts, 28 parts, and 29 parts, but is not limited thereto. The formaldehyde is used in an amount of 25 to 40 parts, preferably 26 to 35 parts, and illustratively 27 parts, 28 parts, 30 parts, 33 parts, 34 parts, but is not limited thereto.
Preferably, the ratio of the phenol to the formaldehyde is 1: (1-1.1), and more preferably 1 (1.02-1.06). The method controls the use amount of formaldehyde to be larger than that of phenol (the molar ratio is 3.13-3.45: 1), can reduce the generation amount of hydroxymethyl in the polycondensation process, is convenient for controlling the properties such as particle size, specific surface area and the like, and can form more pores on the surface of the spherical phenolic resin microspheres through the control, so that the pore volume and the pore diameter are improved, and the adsorption capacity on dioxin is further improved.
The initiator is an important component for catalyzing the condensation polymerization reaction of phenol and formaldehyde, and has great influence on the stability of a system and the quality of a product. In the invention, the initiator can be selected from alkaline substances, and specifically, one or more of diethylamine, triethylamine, triethanolamine, sodium carbonate and sodium hydroxide can be selected. Preferably, triethylamine is selected as the initiator in the invention, which can ensure that the polycondensation reaction is smoothly carried out, and spherical phenolic resin with excellent performances is obtained. The initiator is used in an amount of 0.4 to 2 parts, preferably 0.7 to 1.0 part, and may be exemplified by 0.7 part, 0.8 part, 0.9 part, and 1.0 part, but is not limited thereto.
The water is used to form a dispersion system, which has a large influence on the particle size distribution, pore size, and pore volume of the spherical phenolic resin. Specifically, the amount of water is 30-50 parts, and the solid content of the whole system can be controlled to be 60-70% (namely, the phenol, the formaldehyde, the initiator, the cross-linking agent and the polyvinyl alcohol account for 60-70% of the total mass of the reaction system) by the amount of water. Preferably, the amount of water is 33 to 38 parts. Exemplary may be 34 parts, 35 parts, 37 parts, but not limited thereto.
The polyvinyl alcohol is a good dispersant and stabilizer, and is added into a phenol and formaldehyde polycondensation system, so that the polycondensation process can be effectively stabilized, and various properties of the carbon microspheres, such as particle size, specific surface area, pore volume, pore diameter and the like, can be effectively regulated and controlled. Specifically, the dosage of the polyvinyl alcohol is 1-10 parts, when the dosage is less than 1 part, the phenolic resin formed by polycondensation is blocky, the particle size of the carbon microsphere is too large, and the adsorption capacity is poor; when the amount is more than 10 parts, the surface area is large although the particle size is small; but the pore volume and the pore diameter are relatively small, and the carbon microsphere has poor adsorption capacity to gas-phase dioxin. Preferably, the amount of polyvinyl alcohol is 2 to 6 parts, and more preferably 2 to 3 parts.
The cross-linking agent can be selected from one or more of diethylene triamine, triethylene tetramine, hexamethylene tetramine and hexamethyl phosphoric triamide, but is not limited to the cross-linking agent; preferably, the crosslinking agent is diethylenetriamine. The amount of the cross-linking agent is 2-5 parts, preferably 3-4 parts.
Furthermore, in order to achieve good control over various properties of the carbon microsphere, the preparation method of the invention also needs to be combined. Specifically, referring to fig. 1, the method for preparing carbon microspheres for dioxin adsorption according to the present invention includes the following steps:
s1: uniformly mixing phenol, formaldehyde, an initiator and water, adding polyvinyl alcohol, and reacting at 90-100 ℃ for 0.5-2 h to obtain a prepolymer;
specifically, S1 includes:
s11: adding phenol and formaldehyde into a three-neck flask, and starting stirring;
s12: under the condition of uniform stirring, adding water and an initiator, and continuously stirring until the mixture is uniformly mixed;
specifically, the stirring speed is 300-500 rpm, the stirring speed has obvious influence on the polycondensation reaction, and when the stirring speed is less than 300rpm, the system cannot be well dispersed, and massive phenolic resin is easily formed; when the stirring speed is more than 500rpm, the dispersion strength is too high, which results in too large a particle size distribution range of the spherical phenolic resin and is disadvantageous to the comprehensive performance of the spherical phenolic resin. Preferably, the stirring speed is 400 rpm.
S13: adding polyvinyl alcohol, and reacting at 90-100 ℃ for 0.5-2 h to obtain a prepolymer.
S2: adding a cross-linking agent into the prepolymer, reacting for 1-6 h at 90-100 ℃, and curing to obtain polymer microspheres;
specifically, S2 includes:
s21: adding a cross-linking agent into the prepolymer, reacting for 1-6 h at 90-100 ℃, and curing to obtain an intermediate;
s22: filtering, cleaning and drying the intermediate to obtain polymer microspheres;
s3: carbonizing the polymer microspheres in an inert atmosphere, and then activating in a carbon dioxide atmosphere to obtain the finished carbon microspheres.
Specifically, S3 includes:
s31: carbonizing the polymer microspheres in an inert atmosphere;
specifically, the inert atmosphere is a nitrogen atmosphere or an argon atmosphere, but is not limited thereto. The purities of the nitrogen and the argon are 99.9-99.999%.
Specifically, the carbonization process comprises: and (3) heating the polymer microspheres to 750-950 ℃ at the heating rate of 5-10 ℃/min, and then preserving the heat for 1-5 h (carbonization time).
S32: and activating the carbonized polymer microspheres in a carbon dioxide atmosphere to obtain finished carbon microspheres.
Specifically, the purity of the carbon dioxide is 99.9% -99.999%.
Specifically, the activation process comprises: and after carbonization, introducing carbon dioxide, replacing the inert atmosphere with carbon dioxide atmosphere, then preserving the heat at 750-950 ℃ for 0.5-6 h (activation time), and cooling to room temperature along with the furnace after activation is finished to obtain the finished product of the carbon microsphere for dioxin adsorption.
The carbon microsphere obtained by the formula and the preparation method has the particle size of 1-200 mu m and the specific surface area of 450-2500 m2A pore diameter of 1 to 15nm and a pore volume of 0.5 to 5cm3(ii)/g; it has good adsorption capacity to dioxin. The research shows that the gas-phase dioxin mainly exists in a molecular form, the long axis of the molecule is about 1.2-2 nm, the short axis is about 0.5-1.1 nm, the thickness of the molecule is about 0.2-0.4 nm, and the most effective adsorption pore diameter for the gas-phase dioxin is 1-4 nm and 5-20 nm. According to the invention, the aperture of the carbon microsphere is controlled to be 1-15 nm by regulating and controlling the reaction process, so that the effective adsorption of gas-phase dioxin is realized.
The invention is illustrated below in specific examples:
example 1
The present embodiment provides a carbon microsphere for adsorbing dioxin, which has the following formula:
28.7 parts of phenol, 30.5 parts of formaldehyde, 0.8 part of triethylamine, 34.5 parts of water, 2 parts of polyvinyl alcohol and 3.5 parts of diethylenetriamine.
The preparation method comprises the following steps:
adding phenol and formaldehyde into a 500mL three-neck flask, uniformly mixing, adding triethylamine and deionized water at a constant stirring speed of 400rpm, uniformly mixing, adding polyvinyl alcohol, reacting for 1h at a water bath condition of 97 ℃ under the condition of a stirring speed of 400r/min, then adding diethylenetriamine, and continuing to perform a crosslinking reaction for 4h at the temperature of 97 ℃. Followed by filtration and washing several times with deionized water. And (3) after the obtained sample is subjected to forced air drying at the temperature of 80 ℃ for 12h, keeping the temperature for 3h at the temperature of 850 ℃ under the protection of argon atmosphere, wherein the heating rate is 5 ℃/min, then introducing carbon dioxide gas, and keeping the temperature for 3h, thereby obtaining a finished product of the carbon microsphere for dioxin adsorption.
The carbon microsphere obtained by the embodiment has the particle size of 60-150 mu m and the specific surface area of 1677m2G, pore diameter of about 2.5nm and pore volume of 1.07cm3/g。
The microscopic morphologies of the carbon microspheres obtained by the example are shown in fig. 2 to 3, and it can be seen from the figures that the carbon microspheres of the present invention have a high degree of uniformity in particle size. The adsorption curve of the carbon microsphere is shown in FIG. 4, and the pore size distribution curve is shown in FIG. 5.
Example 2
The present embodiment provides a carbon microsphere for adsorbing dioxin, which has the following formula:
28.5 parts of phenol, 30.1 parts of formaldehyde, 0.8 part of triethylamine, 34.2 parts of water, 3 parts of polyvinyl alcohol and 3.4 parts of diethylenetriamine.
The preparation method comprises the following steps:
adding phenol and formaldehyde into a 500mL three-neck flask, uniformly mixing, adding triethylamine and deionized water at a constant stirring speed of 400rpm, uniformly mixing, adding polyvinyl alcohol, reacting for 1h at a water bath condition of 97 ℃ under the condition of a stirring speed of 400r/min, then adding diethylenetriamine, and continuing to perform a crosslinking reaction for 4h at the temperature of 97 ℃. Followed by filtration and washing several times with deionized water. And (3) after the obtained sample is subjected to forced air drying at the temperature of 80 ℃ for 12h, keeping the temperature for 3h at the temperature of 850 ℃ under the protection of argon atmosphere, wherein the heating rate is 5 ℃/min, then introducing carbon dioxide gas, and keeping the temperature for 6h, thereby obtaining a finished product of the carbon microsphere for dioxin adsorption.
The carbon microsphere obtained by the embodiment has the particle size of 5-30 mu m and the specific surface area of 2436m2G, pore diameter of about 5nm and pore volume of 1.27cm3/g。
Example 3
The present embodiment provides a carbon microsphere for adsorbing dioxin, which has the following formula:
27 parts of phenol, 27 parts of formaldehyde, 0.7 part of triethylamine, 38 parts of water, 4 parts of polyvinyl alcohol and 3.3 parts of diethylenetriamine.
The preparation method comprises the following steps:
adding phenol and formaldehyde into a 500mL three-neck flask, uniformly mixing, adding triethylamine and deionized water at a constant stirring speed of 400rpm, uniformly mixing, adding polyvinyl alcohol, reacting for 40min in a water bath at 97 ℃ under the condition that the stirring speed is 400r/min, then adding diethylenetriamine, and continuing to perform a crosslinking reaction for 4h at 97 ℃. Followed by filtration and washing several times with deionized water. And (3) after the obtained sample is subjected to forced air drying at the temperature of 80 ℃ for 12h, keeping the temperature for 3h at the temperature of 850 ℃ under the protection of argon atmosphere, wherein the heating rate is 5 ℃/min, then introducing carbon dioxide gas, and keeping the temperature for 1h, thereby obtaining a finished product of the carbon microsphere for dioxin adsorption.
The carbon microsphere obtained by the embodiment has the particle size of 3-20 mu m and the specific surface area of 2491m2G, pore diameter of about 7.5nm and pore volume of 0.73cm3/g。
Example 4
The present embodiment provides a carbon microsphere for adsorbing dioxin, which has the following formula:
27 parts of phenol, 27 parts of formaldehyde, 0.7 part of triethylamine, 37.3 parts of water, 5 parts of polyvinyl alcohol and 3 parts of diethylenetriamine.
The preparation method is the same as in example 3.
The carbon microsphere obtained by the embodiment has the particle size of 1-15 mu m and the specific surface area of 2411m2G, pore diameter of about 8.5nm and pore volume of 0.85cm3/g。
Example 5
The present embodiment provides a carbon microsphere for adsorbing dioxin, which has the following formula:
26.5 parts of phenol, 26.5 parts of formaldehyde, 0.7 part of triethylamine, 37.3 parts of water, 6 parts of polyvinyl alcohol and 3 parts of diethylenetriamine.
The preparation method is the same as in example 3.
The carbon microsphere obtained by the embodiment has the particle size of 1-10 mu m and the specific surface area of 2821m2G, pore diameter of about 8.5nm and pore volume of 0.65cm3/g。
Example 6
The present embodiment provides a carbon microsphere for adsorbing dioxin, which has the following formula:
27.2 parts of phenol, 28.8 parts of formaldehyde, 0.8 part of triethylamine, 38.4 parts of water, 1 part of polyvinyl alcohol and 3.8 parts of diethylenetriamine.
The preparation method comprises the following steps:
adding phenol and formaldehyde into a 500mL three-neck flask, uniformly mixing, adding triethylamine and deionized water at a constant stirring speed of 400rpm, uniformly mixing, adding polyvinyl alcohol, reacting for 40min in a water bath at 97 ℃ under the condition that the stirring speed is 400r/min, then adding diethylenetriamine, and continuing to perform a crosslinking reaction for 4h at 97 ℃. Followed by filtration and washing several times with deionized water. And (3) after the obtained sample is subjected to forced air drying at the temperature of 80 ℃ for 12h, keeping the temperature for 3h at the temperature of 850 ℃ under the protection of argon atmosphere, wherein the heating rate is 5 ℃/min, then introducing carbon dioxide gas, and keeping the temperature for 0.5h, thereby obtaining a finished product of the carbon microsphere for dioxin adsorption.
The carbon microsphere obtained by the embodiment has the particle size of 120-200 mu m and the specific surface area of 1103m2Per g, pore diameter of about 5nm and pore volume of 0.57cm3/g。
Test example 1
In this test example, the carbon microsphere prepared in example 1 was used as a medium to perform a dioxin adsorption experiment, specifically, 17 kinds of dioxin (including low-chlorinated dioxin and high-chlorinated dioxin) standard samples were added to the carbon microsphere prepared in example 1, toluene was used as a solvent to collect dioxin adsorbed on the carbon microsphere, and the amount of dioxin adsorbed on the carbon microsphere was quantitatively analyzed by a magnetic mass spectrometer and a gas chromatograph-mass spectrometer, and the result shows that the adsorption rate of the carbon microsphere is as high as 80% or more, and the result is shown in fig. 6.
Comparative test example 1
In the experimental example, the carbon nanotube was used as a medium to perform a dioxin adsorption experiment, specifically, 17 kinds of dioxins were subjected to an adsorption experiment, the experimental process was consistent with that of experimental example 1, and the detection result showed that the carbon nanotube has an adsorption rate of about 57%, as shown in fig. 7.
Comparative test example 2
In the experimental example, activated carbon is used as a medium to perform a dioxin adsorption experiment, specifically, 17 kinds of dioxin are subjected to an adsorption experiment, the experimental process is consistent with that of experimental example 1, and the detection result shows that the activated carbon has an adsorption rate of about 51%, as shown in fig. 8.
As can be seen from comparison between test example 1 and comparative test examples 1 and 2, the adsorption capacity of the carbon microspheres of the present invention to dioxin was higher than that of carbon nanotubes and activated carbon by 20% or more.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.

Claims (10)

1. The carbon microsphere for adsorbing dioxin is characterized by being mainly prepared from the following raw materials in parts by weight:
25-35 parts of phenol, 25-40 parts of formaldehyde, 0.4-2 parts of an initiator, 30-50 parts of water, 1-10 parts of polyvinyl alcohol and 2-5 parts of a cross-linking agent;
the sum of the parts by weight of the phenol, the formaldehyde, the initiator, the water, the polyvinyl alcohol and the cross-linking agent is 100 parts;
the preparation method comprises the following steps:
(1) uniformly mixing phenol, formaldehyde, an initiator and water, adding polyvinyl alcohol, and reacting at 90-100 ℃ for 0.5-2 h to obtain a prepolymer;
(2) adding a cross-linking agent into the prepolymer, reacting at 90-100 ℃ for 1-6 h, and curing to obtain polymer microspheres;
(3) carbonizing the polymer microspheres in an inert atmosphere, and then activating in a carbon dioxide atmosphere to obtain the finished carbon microspheres.
2. The carbon microsphere for dioxin adsorption according to claim 1, wherein the weight ratio of phenol to formaldehyde is 1: (1-1.1).
3. The carbon microsphere for adsorbing dioxin according to claim 1, wherein the initiator is one or more selected from diethylamine, triethylamine, triethanolamine, sodium carbonate, and sodium hydroxide;
4. the carbon microsphere for dioxin adsorption according to claim 1, wherein the crosslinking agent is one or more selected from the group consisting of diethylenetriamine, triethylenetetramine, hexamethylenetetramine, and hexamethylphosphoric triamide.
5. The carbon microsphere for adsorbing dioxin according to any one of claims 1 to 4, wherein the initiator is triethylamine and the crosslinking agent is diethylenetriamine.
6. The carbon microsphere for dioxin adsorption according to claim 1, which is prepared from the following raw materials in parts by weight:
26-30 parts of phenol, 26-35 parts of formaldehyde, 0.7-1.0 part of triethylamine, 33-38 parts of water, 2-6 parts of polyvinyl alcohol and 3-4 parts of diethylenetriamine;
the total weight of phenol, formaldehyde, triethylamine, water, polyvinyl alcohol and diethylenetriamine is 100 parts;
7. the carbon microsphere for dioxin adsorption according to claim 1, wherein in step (3), the polymer microsphere is carbonized in an argon or nitrogen atmosphere at a carbonization temperature of 750 to 950 ℃ for 1 to 5 hours at a temperature rise rate of 5 to 10 ℃/min during carbonization.
8. The carbon microsphere for dioxin adsorption according to claim 7, wherein in step (3), the activation temperature is 750 to 950 ℃ and the activation time is 0.5 to 6 hours.
9. The carbon microsphere for dioxin adsorption according to claim 8, wherein the purity of the nitrogen, argon, carbon dioxide is 99.9 to 99.999%.
10. The carbon microsphere for dioxin adsorption according to claim 9, wherein the carbon microsphere has a particle diameter of 1 to 200 μm and a specific surface area of 1100 to 2900m2A pore diameter of 1 to 15nm and a pore volume of 0.5 to 5cm3/g。
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