CN111905695A - Cellulose-based hollow porous carbon fiber microsphere adsorbent and preparation method thereof - Google Patents
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Abstract
The invention relates to a cellulose-based hollow porous carbon fiber microsphere adsorbent and a preparation method thereof, which are characterized in that cellulose is used as a raw material and is prepared into hollow porous microspheres, the hollow porous carbon fiber microspheres are prepared by adopting a carbonization technology, and the microspheres are dissolved in dopamine hydrochloride to obtain dopamine hydrochloride modified hollow porous carbon fiber microspheres. The removal rate of 0.5mg/L formaldehyde gas by the cellulose-based hollow porous carbon fiber microspheres prepared by the method reaches over 80 percent; saturated adsorption capacity of the dopamine hydrochloride modified hollow porous carbon fiber microspheres to cadmium ions and lead ions is 183.9-189.3 mg/g and 256.7-265.3 mg/g respectively. The preparation method is simple, and the production process has no pollution to the environment.
Description
Technical Field
The invention belongs to the technical field of carbon fiber microspheres, and particularly relates to a cellulose-based hollow porous carbon fiber microsphere adsorbent and a preparation method thereof.
Background
The microspheres are particles with small particle size, the diameters of the particles are distributed in the range of 1 mu m-3 mm, and cellulose, chitin, lignin and the like are prepared into the microspheres and are widely applied to various fields. The special advantages of the microspheres are particularly prominent in many fields, the microspheres of various materials such as bamboo shoots gush out after raining, and among many microspheres, the carbon fiber microspheres have not been reported yet. Carbon fiber, as a novel material, has advantages of a large specific surface area, a light specific gravity, and the like, and has received much attention in various fields.
Heavy metal pollution in water has become an important factor of contemporary environmental pollution, heavy metal ions, such as: cadmium ions, lead ions, zinc ions, copper ions, manganese ions, nickel ions, and the like are discharged in the natural world in industrial production. Heavy metals cannot be decomposed and, if they accumulate in the organism, are seriously harmful to the organism. In addition, indoor formaldehyde pollution is also an important factor influencing the health of people, and particularly, the hidden trouble of overhigh formaldehyde concentration exists in newly decorated houses. Therefore, the removal of heavy metal ions in water and formaldehyde gas in air in a new room is a problem to be solved urgently. The adsorption technology is a good method for removing heavy metal ions in water and formaldehyde gas in air in a new house.
Currently, various adsorbent materials are various, and many reports on research on adsorbent materials are provided. Chinese patent application No. 201210334217.7 discloses a porous cellulose microsphere adsorbent for blood perfusion and a preparation method thereof; chinese patent application No. 201210097215.0 discloses a cross-linked chitosan microsphere heavy metal adsorbent, which is prepared by preparing microspheres from chitosan, and grafting 2-chloromethyl benzimidazole on the microspheres. From the research of literature reports, many natural products are manufactured into microspheres, and then the microspheres can be used as adsorbents after being chemically modified. However, studies on the use of carbon fiber microspheres as adsorbents have been rarely reported. Carbon fiber materials have many advantages, such as: large surface area, light specific gravity, many active sites and the like, and is widely applied in many fields, and the application of the adsorbent material in the field of adsorbent materials needs to be further researched.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a cellulose-based hollow porous carbon fiber microsphere adsorbent and a preparation method thereof. The hollow porous carbon fiber microsphere adsorbent prepared by the invention has good adsorption performance on formaldehyde gas, and the dopamine hydrochloride modified hollow porous carbon fiber microsphere adsorbent has good adsorption performance on heavy metal ions (cadmium ions and lead ions).
The invention aims to provide a cellulose-based hollow porous carbon fiber microsphere adsorbent, which is characterized in that cellulose is used as a raw material, the cellulose is firstly prepared into hollow porous microspheres, then the hollow porous carbon fiber microsphere adsorbent is prepared by adopting a carbonization technology, and finally the microspheres are dissolved in dopamine hydrochloride to obtain the modified hollow porous carbon fiber microsphere adsorbent.
Another object of the present invention is to provide a preparation method of the cellulose-based hollow porous carbon fiber microsphere adsorbent, wherein the preparation method comprises the following steps:
the method comprises the following steps: alternately cleaning the cellulose-based hollow porous microspheres for 3 times by using deionized water and absolute ethyl alcohol, and drying the cleaned cellulose-based hollow porous microspheres in an oven at 80 ℃ for 2-3 h;
step two: putting the cellulose-based hollow porous microspheres treated in the step one into a 800-1000 ℃ tubular furnace, and carbonizing for 2-3 hours under the condition of nitrogen atmosphere;
step three: washing and drying the cellulose-based hollow porous carbon fiber microspheres treated in the step two by using deionized water;
step four: placing the cellulose-based hollow porous carbon fiber microspheres prepared in the step three into an ultrasonic generator for treatment, wherein the medium is water, and the treatment time is 1-3 hours; after the treatment is finished, putting the mixture into clear water to quickly cool the mixture, and drying the mixture for later use;
step five: and (3) dissolving the cellulose-based hollow porous carbon fiber microspheres processed in the fourth step in 5-10 mg/mL dopamine hydrochloride Tris buffer solution, oscillating for 2-3 h at room temperature in a dark environment, separating the product, washing for 2-3 times by using ultrapure water and ethanol, and drying to obtain the product.
The preparation method of the cellulose-based hollow porous carbon fiber microsphere adsorbent comprises the following steps:
step 101: preparation of oil-in-water emulsion: swelling cellulose in glacial acetic acid for 2-4 h, dissolving the cellulose in a mixed solution of acetic anhydride and acetic acid, dropwise adding sulfuric acid into the system, reacting for 2-5 h at 55 ℃, neutralizing the sulfuric acid in the system with sodium hydroxide to pH 7-8 after the reaction is finished, pouring the reactant into distilled water to precipitate cellulose acetate, centrifuging and washing the obtained cellulose acetate for multiple times to be neutral, and performing vacuum drying, wherein preferably, the volume ratio of acetic anhydride to acetic acid is 1: 1-1.5, and the use amount of sulfuric acid is 1.0-1.5% of the total volume of acetic anhydride and acetic acid; dissolving the obtained dry cellulose acetate in dichloromethane to obtain a clear and transparent solution, adding span 80 into the solution, stirring and mixing uniformly, adding the mixed solution into an aqueous solution of sodium dodecyl sulfate, and continuously stirring to obtain an oil-in-water emulsion, wherein preferably, the weight ratio of the cellulose acetate to the span 80 is 1: 0.1-0.15, and the volume ratio of the dichloromethane to the aqueous solution of the sodium dodecyl sulfate is 1: 5-7; the mass fraction of the sodium dodecyl sulfate aqueous solution is 0.75-1.0%;
step 102: preparing hollow porous cellulose microspheres: slowly evaporating dichloromethane in the oil-in-water emulsion under a controlled condition, evaporating for 4-6 hours, carrying out centrifugal separation on an evaporation residue to obtain cellulose microspheres, washing the obtained cellulose microspheres with distilled water to remove sodium dodecyl sulfate in the cellulose microspheres, then washing the cellulose microspheres with ethanol for multiple times to remove span 80, and finally carrying out vacuum drying to obtain pure hollow porous cellulose microspheres, wherein the hollow porous cellulose microspheres are shown in figure 1.
The invention has the following remarkable characteristics:
(1) the cellulose-based hollow porous carbon fiber microsphere is prepared, and the specific surface area of the cellulose-based hollow porous carbon fiber microsphere can be obviously increased by the hollow aperture inside the cellulose-based hollow porous carbon fiber microsphere; the carbon fiber microspheres have good adsorption performance on formaldehyde, and the dopamine hydrochloride modified carbon fiber microspheres have good adsorption performance on heavy metal ions. The preparation method is simple, has no pollution to the environment, and has strong market popularization prospect.
(2) The specific surface area of the cellulose-based hollow porous carbon fiber microspheres prepared by the method reaches 60m2The large specific surface area provides more adsorption sites for it.
(3) The removal rate of 0.5mg/L formaldehyde gas of the cellulose-based hollow porous carbon fiber microspheres prepared by the method reaches over 80 percent; saturated adsorption capacity of the dopamine hydrochloride modified carbon fiber microspheres to cadmium ions and lead ions is 183.9-189.3 mg/g and 256.7-265.3 mg/g respectively.
Drawings
FIG. 1 schematic view of hollow porous cellulose microspheres
Detailed Description
The examples described below illustrate the invention in detail.
Example 1
In this embodiment, the preparation method of the cellulose-based hollow porous carbon fiber microsphere adsorbent includes the following steps:
the method comprises the following steps: alternately cleaning the cellulose-based hollow porous microspheres with deionized water and absolute ethyl alcohol for 3 times, and drying the cleaned cellulose-based hollow porous microspheres in an oven at 80 ℃ for 2.5 hours;
step two: putting the cellulose-based hollow porous microspheres treated in the step one into a 900 ℃ tubular furnace, and carbonizing for 2.5 hours under the condition of nitrogen atmosphere;
step three: washing and drying the cellulose-based hollow porous carbon fiber microspheres treated in the step two by using deionized water;
step four: putting the cellulose-based hollow porous carbon fiber microspheres prepared in the step three into an ultrasonic generator for treatment, wherein the medium is water, and the treatment time is 2 hours; after the treatment is finished, putting the mixture into clear water to quickly cool the mixture, and drying the mixture to obtain a product a 1;
step five: and (3) dissolving the cellulose-based hollow porous carbon fiber microspheres processed in the fourth step in 8mg/mL dopamine hydrochloride Tris buffer solution, shaking at room temperature for 2.5h in a dark environment, separating the product, washing the product for 2 times by using ultrapure water and ethanol, and then drying to obtain a product a 2.
The preparation method of the cellulose-based hollow porous carbon fiber microsphere adsorbent comprises the following steps:
step 101: preparation of oil-in-water emulsion: swelling cellulose in glacial acetic acid for 3h, dissolving the cellulose in a mixed solution of acetic anhydride and acetic acid, dropwise adding sulfuric acid into the system, reacting for 4h at 55 ℃, neutralizing the sulfuric acid in the system with sodium hydroxide after the reaction is finished to pH 7-8, then pouring the reactant into distilled water to precipitate cellulose acetate, finally centrifuging and washing the obtained cellulose acetate for multiple times to neutrality, and performing vacuum drying, wherein preferably, the volume ratio of acetic anhydride to acetic acid is 1: 1.2, and the use amount of the sulfuric acid is 1.2% of the total volume of the acetic anhydride and the acetic acid; dissolving the obtained dry cellulose acetate in dichloromethane to obtain a clear and transparent solution, adding span 80 into the solution, stirring and mixing uniformly, adding the mixed solution into an aqueous solution of sodium dodecyl sulfate, and continuously stirring to obtain an oil-in-water emulsion, wherein preferably, the weight ratio of the cellulose acetate to the span 80 is 1: 0.12, and the volume ratio of the dichloromethane to the aqueous solution of the sodium dodecyl sulfate is 1: 6; the mass fraction of the sodium dodecyl sulfate aqueous solution is 0.8 percent;
step 102: preparing hollow porous cellulose microspheres: slowly evaporating dichloromethane in the oil-in-water emulsion under a controlled condition, evaporating for 5h, performing centrifugal separation on an evaporation residue to obtain cellulose microspheres, washing the obtained cellulose microspheres with distilled water to remove sodium dodecyl sulfate therein, then washing with ethanol for multiple times to remove span 80, and finally performing vacuum drying to obtain pure hollow porous cellulose microspheres.
Example 2
In this embodiment, the preparation method of the cellulose-based hollow porous carbon fiber microsphere adsorbent includes the following steps:
the method comprises the following steps: alternately cleaning the cellulose-based hollow porous microspheres with deionized water and absolute ethyl alcohol for 3 times, and drying the cleaned cellulose-based hollow porous microspheres in an oven at 80 ℃ for 2 hours;
step two: putting the cellulose-based hollow porous microspheres treated in the step one into a 800 ℃ tubular furnace, and carbonizing for 3 hours under the condition of nitrogen atmosphere;
step three: washing and drying the cellulose-based hollow porous carbon fiber microspheres treated in the step two by using deionized water;
step four: placing the cellulose-based hollow porous carbon fiber microspheres prepared in the step three into an ultrasonic generator for treatment, wherein the medium is water, and the treatment time is 1-3 hours; after the treatment is finished, putting the mixture into clear water to quickly cool the mixture, and drying the mixture to obtain a product b 1;
step five: and (3) dissolving the cellulose-based hollow porous carbon fiber microspheres processed in the fourth step in 10mg/mL dopamine hydrochloride Tris buffer solution, shaking at room temperature for 3h in a dark environment, separating the product, washing the product for 3 times by using ultrapure water and ethanol, and drying to obtain a product b 2.
The preparation method of the cellulose-based hollow porous carbon fiber microsphere adsorbent comprises the following steps:
step 101: preparation of oil-in-water emulsion: swelling cellulose in glacial acetic acid for 4h, dissolving the cellulose in a mixed solution of acetic anhydride and acetic acid, dropwise adding sulfuric acid into the system, reacting for 5h at 55 ℃, neutralizing the sulfuric acid in the system with sodium hydroxide after the reaction is finished to pH 7-8, then pouring the reactant into distilled water to precipitate cellulose acetate, finally centrifuging and washing the obtained cellulose acetate for multiple times to neutrality, and performing vacuum drying, wherein preferably, the volume ratio of acetic anhydride to acetic acid is 1: 1.5, and the use amount of the sulfuric acid is 1.5 percent of the total volume of the acetic anhydride and the acetic acid; dissolving the obtained dry cellulose acetate in dichloromethane to obtain a clear and transparent solution, adding span 80 into the solution, stirring and mixing uniformly, adding the mixed solution into an aqueous solution of sodium dodecyl sulfate, and continuously stirring to obtain an oil-in-water emulsion, wherein preferably, the weight ratio of the cellulose acetate to the span 80 is 1: 0.15, and the volume ratio of the dichloromethane to the aqueous solution of the sodium dodecyl sulfate is 1: 7; the mass fraction of the sodium dodecyl sulfate aqueous solution is 1.0 percent;
step 102: preparing hollow porous cellulose microspheres: slowly evaporating dichloromethane in the oil-in-water emulsion under a controlled condition, evaporating for 6 hours, carrying out centrifugal separation on an evaporation residue to obtain cellulose microspheres, washing the obtained cellulose microspheres with distilled water to remove sodium dodecyl sulfate in the cellulose microspheres, then washing the cellulose microspheres with ethanol for multiple times to remove span 80, and finally carrying out vacuum drying to obtain pure hollow porous cellulose microspheres.
Example 3
In this embodiment, the preparation method of the cellulose-based hollow porous carbon fiber microsphere adsorbent includes the following steps:
the method comprises the following steps: alternately cleaning the cellulose-based hollow porous microspheres with deionized water and absolute ethyl alcohol for 3 times, and drying the cleaned cellulose-based hollow porous microspheres in an oven at 80 ℃ for 2 hours;
step two: putting the cellulose-based hollow porous microspheres treated in the step one into a 1000 ℃ tubular furnace, and carbonizing for 2 hours under the condition of nitrogen atmosphere;
step three: washing and drying the cellulose-based hollow porous carbon fiber microspheres treated in the step two by using deionized water;
step four: putting the cellulose-based hollow porous carbon fiber microspheres prepared in the step three into an ultrasonic generator for treatment, wherein the medium is water, and the treatment time is 3 hours; after the treatment is finished, putting the mixture into clear water to quickly cool the mixture, and drying the mixture to obtain a product c 1;
step five: and (3) dissolving the cellulose-based hollow porous carbon fiber microspheres processed in the fourth step in 5mg/mL dopamine hydrochloride Tris buffer solution, shaking for 2h at room temperature in a dark environment, separating the product, washing for 3 times by using ultrapure water and ethanol, and drying to obtain a product c 2.
The preparation method of the cellulose-based hollow porous carbon fiber microsphere adsorbent comprises the following steps:
step 101: preparation of oil-in-water emulsion: swelling cellulose in glacial acetic acid for 4h, dissolving the cellulose in a mixed solution of acetic anhydride and acetic acid, dropwise adding sulfuric acid into the system, reacting for 5h at 55 ℃, neutralizing the sulfuric acid in the system with sodium hydroxide after the reaction is finished to pH 7-8, then pouring the reactant into distilled water to precipitate cellulose acetate, finally centrifugally washing the obtained cellulose acetate for multiple times to neutrality, and performing vacuum drying, wherein preferably, the volume ratio of acetic anhydride to acetic acid is 1: 1, and the use amount of the sulfuric acid is 1.0 percent of the total volume of the acetic anhydride and the acetic acid; dissolving the obtained dry cellulose acetate in dichloromethane to obtain a clear and transparent solution, adding span 80 into the solution, stirring and mixing uniformly, adding the mixed solution into an aqueous solution of sodium dodecyl sulfate, and continuously stirring to obtain an oil-in-water emulsion, wherein preferably, the weight ratio of the cellulose acetate to the span 80 is 1: 0.1, and the volume ratio of the dichloromethane to the aqueous solution of the sodium dodecyl sulfate is 1: 5; the mass fraction of the sodium dodecyl sulfate aqueous solution is 0.75 percent;
step 102: preparing hollow porous cellulose microspheres: slowly evaporating dichloromethane in the oil-in-water emulsion under a controlled condition, evaporating for 4 hours, carrying out centrifugal separation on an evaporation residue to obtain cellulose microspheres, washing the obtained cellulose microspheres with distilled water to remove sodium dodecyl sulfate in the cellulose microspheres, then washing the cellulose microspheres with ethanol for multiple times to remove span 80, and finally carrying out vacuum drying to obtain pure hollow porous cellulose microspheres.
Performance test example:
formaldehyde gas adsorption test: and (2) taking a 500mL gas collection bottle as a reaction device, stabilizing the formaldehyde concentration of the gas collection bottle to be 0.5mg/L, adding the hollow porous carbon fiber microspheres prepared by the invention into the bottle, and testing the formaldehyde concentration after 2 hours, wherein the formaldehyde concentration testing method refers to national standard (GB/T18204.2-2014) phenol reagent spectrophotometer. The test results are set forth in table 1: wherein the formaldehyde removal rate R ═ (C)0－C)/C0。
Table 1 adsorption performance of cellulose-based hollow porous carbon fiber microspheres (a1, b1, c1) and dopamine hydrochloride-modified carbon fiber microspheres (a2, b2, c2) prepared according to the present invention on formaldehyde gas
| Item | a1 | a2 | b1 | b2 | c1 | c2 |
| Removal rate | 80.1％ | 2.3％ | 82.3％ | 3.6％ | 81.5％ | 2.2％ |
As can be seen from table 1, the removal rate of 0.5mg/L formaldehyde gas by the cellulose-based hollow porous carbon fiber microspheres (a1, b1, c1) reaches more than 80%, while the adsorption performance of the dopamine hydrochloride modified carbon fiber microspheres (a2, b2, c2) to formaldehyde is poor.
Heavy metal ion adsorption test: at the temperature of 20 ℃, the microspheres prepared by the method are added into a conical flask, then the prepared heavy metal ion solutions with different concentrations are added into a water bath constant temperature oscillator for oscillation, after adsorption reaches 2 hours, the supernatant is taken to measure the concentration of the residual cadmium ions, the saturated adsorption quantity is calculated, and the test results are shown in table 2.
Table 2 adsorption performance of cellulose-based hollow porous carbon fiber microspheres (a1, b1, c1) and dopamine hydrochloride-modified carbon fiber microspheres (a2, b2, c2) prepared according to the present invention on heavy metal ions (cadmium ions and lead ions)
As can be seen from Table 2, the saturated adsorption amounts of the cellulose-based hollow porous carbon fiber microspheres (a1, b1 and c1) to cadmium ions and lead ions are 36.7-38.4 mg/g and 47.3-49.1 mg/g respectively, and the saturated adsorption amounts of the hydrochloric acid dopamine modified carbon fiber microspheres (a2, b2 and c2) to cadmium ions and lead ions are 183.9-189.3 mg/g and 256.7-265.3 mg/g respectively.
Claims (3)
1. The preparation method of the cellulose-based hollow porous carbon fiber microsphere adsorbent is characterized by comprising the following steps of:
the method comprises the following steps: alternately cleaning the cellulose-based hollow porous microspheres for 3 times by using deionized water and absolute ethyl alcohol, and drying the cleaned cellulose-based hollow porous microspheres in an oven at 80 ℃ for 2-3 h;
the preparation method of the cellulose-based hollow porous microspheres in the first step comprises the following steps:
step 101: preparation of oil-in-water emulsion: swelling cellulose in glacial acetic acid for 2-4 h, dissolving the cellulose in a mixed solution of acetic anhydride and acetic acid, dropwise adding sulfuric acid into the system, reacting for 2-5 h at 55 ℃, neutralizing the sulfuric acid in the system with sodium hydroxide to pH 7-8 after the reaction is finished, then pouring the reactant into distilled water to precipitate cellulose acetate, finally centrifugally washing the obtained cellulose acetate for multiple times to neutrality, and performing vacuum drying, wherein the use amount of the sulfuric acid is 1.0-1.5% of the total volume of the acetic anhydride and the acetic acid; dissolving the obtained dry cellulose acetate in dichloromethane to obtain a clear and transparent solution, adding span 80 into the solution, stirring and mixing uniformly, adding the mixed solution into an aqueous solution of sodium dodecyl sulfate, and continuously stirring to obtain an oil-in-water emulsion; the volume ratio of acetic anhydride to acetic acid is 1: 1-1.5, the weight ratio of cellulose acetate to span 80 is 1: 0.1-0.15, and the volume ratio of dichloromethane to sodium dodecyl sulfate aqueous solution is 1: 5-7; the mass fraction of the sodium dodecyl sulfate aqueous solution is 0.75-1.0%;
step 102: preparing hollow porous cellulose microspheres: slowly evaporating dichloromethane in the oil-in-water emulsion under a controlled condition, evaporating for 4-6 hours, carrying out centrifugal separation on an evaporation residue to obtain cellulose microspheres, washing the obtained cellulose microspheres with distilled water to remove sodium dodecyl sulfate in the cellulose microspheres, then washing the cellulose microspheres with ethanol for multiple times to remove span 80, and finally carrying out vacuum drying to obtain pure hollow porous cellulose microspheres;
step two: putting the cellulose-based hollow porous microspheres treated in the step one into a tubular furnace, and carbonizing for 2-3 hours under the condition of nitrogen atmosphere, wherein the temperature of the tubular furnace is as follows: 800-1000 ℃;
step three: washing and drying the cellulose-based hollow porous carbon fiber microspheres treated in the step two by using deionized water;
step four: placing the cellulose-based hollow porous carbon fiber microspheres prepared in the step three into an ultrasonic generator for treatment, wherein the medium is water, and the treatment time is 1-3 hours; after the treatment is finished, putting the mixture into clear water to quickly cool the mixture, and drying the mixture for later use;
step five: and (3) dissolving the cellulose-based hollow porous carbon fiber microspheres processed in the fourth step in a dopamine hydrochloride Tris buffer solution, shaking at room temperature for 2-3 hours in a dark environment, separating the product, washing the product for 2-3 times by using ultrapure water and ethanol, and then drying to obtain the product.
2. The method for preparing the cellulose-based hollow porous carbon fiber microsphere adsorbent according to claim 1, wherein: in the fifth step, the concentration of dopamine hydrochloride is as follows: 5-10 mg/mL.
3. The cellulose-based hollow porous carbon fiber microsphere adsorbent is characterized by being prepared by the preparation method of the cellulose-based hollow porous carbon fiber microsphere adsorbent according to any one of claims 1-2.
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| CN113926431A (en) * | 2021-11-29 | 2022-01-14 | 苏州工业园区安泽汶环保技术有限公司 | Dopamine-containing formaldehyde-removing material and preparation method thereof |
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| CN115722198A (en) * | 2022-10-18 | 2023-03-03 | 北京林业大学 | Preparation and application of metal ion doped aminated lignin-based dye adsorbent |
| CN115722198B (en) * | 2022-10-18 | 2024-01-26 | 北京林业大学 | Preparation and application of metal ion doped aminated lignin-based dye adsorbent |
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