CN113786808B - Preparation method of high-density porous carbon fiber adsorbent - Google Patents
Preparation method of high-density porous carbon fiber adsorbent Download PDFInfo
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Abstract
The invention provides a preparation method of a high-density porous carbon fiber adsorbent, which comprises the following steps: a layer of graphite fiber is flatly laid, a layer of phenolic resin powder is covered, and the graphite fiber and the phenolic resin powder are layered; forming a blank; carbonizing and activating; electrolyzing alkali liquor; cleaning and drying; and (4) carrying out amination modification to obtain the high-density porous carbon fiber adsorbent. The phenolic resin powder is used, so that the adhesive force is strong, the carbon residue rate is high, the phenolic resin powder has a longer storage period than a resin liquid, the use amount is small, the price is low, and less waste is generated; the front process uses a dry process, has short flow and simple process, does not need to add other additives such as a binder and the like, and saves the cost and the forming time; and then, alkaline solution electrolysis is adopted, so that the surface of the graphite fiber contains nitrogen-containing functional groups such as imino, amino and the like, on one hand, the electronegativity of the graphite fiber is improved, on the other hand, conditions are provided for amination, and the modified high-density porous carbonaceous adsorbent has stronger adsorption effect on heavy metal ions.
Description
Technical Field
The invention belongs to the field of environmental remediation, and particularly relates to a preparation method of a high-density porous carbon fiber adsorbent.
Background
With the rapid development of economy in China and the acceleration of the modern industrial process, heavy metals become one of the problems harming the environmental development and human life gradually. The wastewater containing heavy metals causes great harm to the living environment of human beings, and heavy metal ions are discharged along with the wastewater, so that even if the concentration of the heavy metal ions is very low, the heavy metal ions can cause public nuisance and serious environmental pollution, thereby affecting the health of people. Therefore, the research on how to reduce the content of heavy metals in the wastewater and reduce the pollution of the heavy metals to the environment has great significance. At present, the methods for removing heavy metals in wastewater mainly comprise 3 methods: firstly, removing heavy metal ions in the wastewater by chemical reaction; secondly, the heavy metals in the wastewater are adsorbed, concentrated and separated under the condition of not changing the chemical form of the heavy metals; and thirdly, removing heavy metals in the wastewater by the aid of flocculation, absorption, accumulation, enrichment and other actions of microorganisms or plants. Among all the methods, the adsorption method has the characteristics of large adsorption capacity, high speed, high efficiency, simple operation and the like, and has a special position in the field of wastewater treatment. Among them, the adsorption of heavy metal ions by activated carbon is a common means. And the heavy metal ions in the wastewater are adsorbed by a physical adsorption mode by utilizing the characteristic of high specific surface area of the activated carbon. However, the traditional fixed bed is used for adsorption, the bed resistance is large, the energy consumption is large, the operating cost is high, and carbon particles are easy to drop and easily form another particle pollution.
Compared with activated carbon, the graphite fiber has the following advantages: (1) the specific surface area is about two orders of magnitude larger than that of active carbon, the adsorption sites are more, and the adsorption capacity is large; (2) the graphite fiber adsorption material has the advantages of small aperture, short adsorption and desorption stroke due to radial holes, high adsorption and desorption speed block (about 10-100 times of activated carbon), (3) high treatment speed, miniaturization and high efficiency of equipment, and (4) high strength, less dust and no secondary pollution, so the graphite fiber is a novel adsorption material with high efficiency and wide application range.
Disclosure of Invention
The technical problem to be solved is as follows: the invention takes graphite felt leftover materials as raw materials, after opening, the graphite felt leftover materials are paved with phenolic resin layer by layer, and the graphite felt leftover materials are obtained after molding, carbonization, electrolysis and modification; electrolyzing with alkaline solution to make the surface contain imino (-NH) and amino (-NH)2) And the nitrogen-containing functional groups improve the electronegativity of the graphite fiber on one hand, and provide conditions for amination on the other hand, and the modified high-density porous carbonaceous adsorbent has stronger adsorption effect on heavy metal ions.
The technical scheme is as follows: a high density porous carbon fiber adsorbent comprising the steps of:
opening the graphite felt leftover materials by using an opener to obtain graphite fibers;
step (2), a layer of graphite fiber is flatly laid, a layer of phenolic resin powder is covered, and the graphite fiber and the phenolic resin powder are layered;
step (3), blank forming: drying and forming the laid materials;
step (4), carbonization and activation: carbonizing and activating the mixture in a nitrogen atmosphere to obtain a carbon fiber adsorbent;
and (5) electrolyzing alkali liquor: taking a mixed solution of ammonium bicarbonate and p-phenylenediamine as an electrolyte, and electrolyzing the surface of the activated carbon fiber adsorbent; the electrolytic bath of alkaline solution used in the electrolysis is shown in FIG. 2.
And (6) cleaning: nitrogen bubbling cleaning is carried out in a water washing tank, the carbon fiber adsorbent after electrolysis is washed until the conductivity of effluent is less than or equal to 90us/cm, and the carbon fiber adsorbent is taken out and dried to obtain porous carbon fiber adsorbent;
soaking 5-10 parts of porous carbon fiber adsorbent in 100 parts of 15% sodium hydroxide solution, stirring in an ice water bath at 0-4 ℃, sequentially adding 15 parts of chloroacetic acid and 2-3 parts of ethylenediamine, continuously stirring for 50min, heating to 15 ℃, and stirring for 1 h;
adding 1 part of 30% sodium hydroxide solution in batches each time, adding the next batch after the phenolphthalein indicator does not show alkalinity after each addition, keeping the reactant at room temperature for 12 hours, heating to 85 ℃, adding 200 parts of deionized water, standing for 30 minutes, and naturally cooling to room temperature;
and (9) adding a 5% hydrochloric acid solution, soaking for 12h, washing with deionized water until the supernatant is neutral, and drying in a 60 ℃ oven to obtain the high-density porous carbon fiber adsorbent. The specific steps and material structure are shown in fig. 1.
Further, in the step (2), the mass ratio of the layer of graphite fibers to the layer of phenolic resin powder is as follows: (40-60) and (60-40).
Furthermore, the number of layers of the graphite fibers and the phenolic resin powder in the step (2) is 4-8.
Further, the pressure of the drying and forming in the step (3) is 10-40 MPa, and the temperature is 100-300 ℃.
Further, the activation of carbonization in the step (4) includes high-temperature carbonization and low-temperature carbonization, and the high-temperature carbonization conditions are as follows: 700-1100 ℃ for 30-90 min; the low-temperature carbonization condition is 350-650 ℃ and 20-60 min.
Further, the current density in the step (5) is 0.7-0.9A/100 cm2(ii) a The retention time is 10-15S; the electrolyte concentration is 2% -5% of ammonium bicarbonate and 0.5% -1% of p-phenylenediamine solution; electrolysisThe temperature was 25 ℃.
Has the advantages that:
1. the invention uses the phenolic resin powder, the cohesive force is strong, the carbon residue rate is high, meanwhile, the phenolic resin powder has longer storage period than the resin liquid, the usage amount is less, the price is low, and the produced waste material is less.
2. The preparation method adopts a dry process, has short flow, simple process and easy operation, does not need to add other additives such as a binder, a curing agent and the like, and saves the cost and the forming time.
3. The invention uses graphite fiber as matrix, which has high strength, small thermal expansion coefficient, no shrinkage at high temperature and no oxygen-containing active group on the surface, and avoids the cracking and stripping phenomena caused by overlarge interface stress when the fiber and phenolic resin are carbonized and activated. Since the two-phase interface between the fiber and the resin is more strongly bonded if the oxygen-containing active group is present, the resin is easily peeled off as the thermal stress generated by shrinkage due to pyrolysis of the matrix resin during carbonization becomes larger.
4. The invention adopts alkaline solution electrolysis to lead the surface of the material to contain imino (-NH) and amino (-NH)2) And the nitrogen-containing functional groups improve the electronegativity of the graphite fiber on one hand, and provide conditions for amination on the other hand, and the modified high-density porous carbonaceous adsorbent has stronger adsorption effect on heavy metal ions.
5. The prepared porous carbon fiber adsorbent has high strength, high density and strong adsorption capacity, and carbon powder is not easy to fall off;
6. the invention takes the graphite felt leftover material as the raw material, recycles waste, has high added value and changes waste into valuable.
Description of the drawings:
FIG. 1 is a flow chart of the structure and steps of the present invention;
FIG. 2 is a schematic view of an alkaline solution electrolytic cell for use in electrolysis of the present invention.
In the figure: 1. an anode plate; 2. a cathode plate; 3. a 24V DC power supply; 4. an RPVC tank body; 5. electrolyzing the solution; 6. a PVC grid tray; 7. a carbon fiber adsorbent.
Detailed Description
Example 1
A preparation method of a high-density porous carbon fiber adsorbent comprises the following steps:
opening the graphite felt leftover materials by using an opener to obtain graphite fibers;
step (2), a layer of graphite fiber is flatly laid, a layer of phenolic resin powder is covered, the graphite fiber and the phenolic resin powder are layered, and the modified graphite felt leftover material and the phenolic resin powder are in the following mass ratio: 40: 60; the number of layers of the modified graphite felt leftover material and the phenolic resin powder is 4 in total;
step (3), blank forming: drying and molding the laid materials at the pressure of 10MPa and the temperature of 300 ℃;
and (4) high-temperature carbonization and activation: under the nitrogen atmosphere, carbonizing and activating to obtain the carbon fiber adsorbent, wherein the high-temperature carbonization conditions are as follows: at 700 ℃ for 30 min;
and (5) electrolyzing alkali liquor: the mixed solution of ammonium bicarbonate and p-phenylenediamine is used as electrolyte to electrolyze the surface of the activated carbon fiber adsorbent, wherein the current density is 0.7A/100cm2(ii) a The retention time is 10S; the electrolyte concentration is 2% ammonium bicarbonate and 0.5% p-phenylenediamine solution; the electrolysis temperature is 25 ℃;
and (6) cleaning: nitrogen bubbling cleaning is carried out in a water washing tank, the carbon fiber adsorbent after electrolysis is washed until the conductivity of effluent is less than or equal to 90us/cm, and the carbon fiber adsorbent is taken out and dried to obtain porous carbon fiber adsorbent;
soaking 5 parts of porous carbon fiber adsorbent in 100 parts of 15% sodium hydroxide solution, stirring in an ice water bath at 0 ℃, sequentially adding 15 parts of chloroacetic acid and 2 parts of ethylenediamine, continuously stirring for 50min, heating to 15 ℃, and stirring for 1 h;
adding 1 part of 30% sodium hydroxide solution in batches each time, adding the next batch after the phenolphthalein indicator does not show alkalinity after each addition, keeping the reactant at room temperature for 12 hours, heating to 85 ℃, adding 200 parts of deionized water, standing for 30 minutes, and naturally cooling to room temperature;
and (9) adding a 5% hydrochloric acid solution, soaking for 12h, washing with deionized water until the supernatant is neutral, and drying in a 60 ℃ oven to obtain the high-density porous carbon fiber adsorbent.
Example 2
A preparation method of a high-density porous carbon fiber adsorbent comprises the following steps:
opening the graphite felt leftover materials by using an opener to obtain graphite fibers;
step (2), a layer of graphite fiber is flatly laid, a layer of phenolic resin powder is covered, the graphite fiber and the phenolic resin powder are layered, and the modified graphite felt leftover material and the phenolic resin powder are in the following mass ratio: 40: 50; the number of layers of the modified graphite felt leftover material and the phenolic resin powder is 6 in total;
step (3), blank forming: drying and molding the laid materials at the pressure of 20MPa and the temperature of 150 ℃;
step (4), carbonization and activation: under the nitrogen atmosphere, carrying out high-temperature carbonization and activation to obtain the carbon fiber adsorbent, wherein the high-temperature carbonization conditions are as follows: at 800 ℃ for 50 min;
and (5) electrolyzing alkali liquor: the mixed solution of ammonium bicarbonate and p-phenylenediamine is used as electrolyte to electrolyze the surface of the activated carbon fiber adsorbent, wherein the current density is 0.7A/100cm2(ii) a The retention time is 11S; the electrolyte concentration is 3% ammonium bicarbonate and 0.6% p-phenylenediamine solution; the electrolysis temperature is 25 ℃;
and (6) cleaning: nitrogen bubbling cleaning is carried out in a water washing tank, the carbon fiber adsorbent after electrolysis is washed until the conductivity of effluent is less than or equal to 90us/cm, and the carbon fiber adsorbent is taken out and dried to obtain porous carbon fiber adsorbent;
step (7) soaking 6 parts of porous carbon fiber adsorbent in 100 parts of 15% sodium hydroxide solution, stirring in an ice water bath at 1 ℃, sequentially adding 15 parts of chloroacetic acid and 2.5 parts of ethylenediamine, continuously stirring for 50min, heating to 15 ℃, and stirring for 1 h;
adding 1 part of 30% sodium hydroxide solution in batches each time, adding the next batch after the phenolphthalein indicator does not show alkalinity after each addition, keeping the reactant at room temperature for 12 hours, heating to 85 ℃, adding 200 parts of deionized water, standing for 30 minutes, and naturally cooling to room temperature;
and (9) adding a 5% hydrochloric acid solution, soaking for 12h, washing with deionized water until the supernatant is neutral, and drying in a 60 ℃ oven to obtain the high-density porous carbon fiber adsorbent.
Example 3
A preparation method of a high-density porous carbon fiber adsorbent comprises the following steps:
opening the graphite felt leftover materials by using an opener to obtain graphite fibers;
step (2), a layer of graphite fiber is flatly laid, a layer of phenolic resin powder is covered, the graphite fiber and the phenolic resin powder are layered, and the modified graphite felt leftover material and the phenolic resin powder are in the following mass ratio: 40: 40; the number of layers of the modified graphite felt leftover material and the phenolic resin powder is 6 in total;
step (3), blank forming: drying and molding the laid materials at the pressure of 30MPa and the temperature of 200 ℃;
step (4), carbonization and activation: under the nitrogen atmosphere, carrying out high-temperature carbonization and activation to obtain the carbon fiber adsorbent, wherein the high-temperature carbonization conditions are as follows: at 800 ℃ for 90 min;
and (5) electrolyzing alkali liquor: the mixed solution of ammonium bicarbonate and p-phenylenediamine is used as electrolyte to electrolyze the surface of the activated carbon fiber adsorbent, wherein the current density is 0.8A/100cm2(ii) a The retention time is 12S; the electrolyte concentration is 3% ammonium bicarbonate and 0.7% p-phenylenediamine solution; the electrolysis temperature is 25 ℃;
and (6) cleaning: nitrogen bubbling cleaning is carried out in a water washing tank, the carbon fiber adsorbent after electrolysis is washed until the conductivity of effluent is less than or equal to 90us/cm, and the carbon fiber adsorbent is taken out and dried to obtain porous carbon fiber adsorbent;
step (7), soaking 7 parts of porous carbon fiber adsorbent in 100 parts of 15% sodium hydroxide solution, stirring in an ice-water bath at 2 ℃, sequentially adding 15 parts of chloroacetic acid and 2.5 parts of ethylenediamine, continuously stirring for 50min, heating to 15 ℃, and stirring for 1 h;
adding 1 part of 30% sodium hydroxide solution in batches each time, adding the next batch after the phenolphthalein indicator does not show alkalinity after each addition, keeping the reactant at room temperature for 12 hours, heating to 85 ℃, adding 200 parts of deionized water, standing for 30 minutes, and naturally cooling to room temperature;
and (9) adding a 5% hydrochloric acid solution, soaking for 12h, washing with deionized water until the supernatant is neutral, and drying in a 60 ℃ oven to obtain the high-density porous carbon fiber adsorbent.
Example 4
A preparation method of a high-density porous carbon fiber adsorbent comprises the following steps:
opening the graphite felt leftover materials by using an opener to obtain graphite fibers;
step (2), a layer of graphite fiber is flatly laid, a layer of phenolic resin powder is covered, the graphite fiber and the phenolic resin powder are layered, and the modified graphite felt leftover material and the phenolic resin powder are in the following mass ratio: 50: 40; the number of layers of the modified graphite felt leftover material and the phenolic resin powder is 6 in total;
step (3), blank forming: drying and molding the laid materials at the pressure of 30MPa and the temperature of 200 ℃;
step (4), carbonization and activation: under the nitrogen atmosphere, carrying out high-temperature carbonization and activation to obtain the carbon fiber adsorbent, wherein the high-temperature carbonization conditions are as follows: 900 ℃ for 80 min;
and (5) electrolyzing alkali liquor: the mixed solution of ammonium bicarbonate and p-phenylenediamine is used as electrolyte to electrolyze the surface of the activated carbon fiber adsorbent, wherein the current density is 0.8A/100cm2(ii) a The retention time is 13S; the electrolyte concentration is 3% ammonium bicarbonate and 0.8% p-phenylenediamine solution; the electrolysis temperature is 25 ℃;
and (6) cleaning: nitrogen bubbling cleaning is carried out in a water washing tank, the carbon fiber adsorbent after electrolysis is washed until the conductivity of effluent is less than or equal to 90us/cm, and the carbon fiber adsorbent is taken out and dried to obtain porous carbon fiber adsorbent;
step (7), soaking 8 parts of porous carbon fiber adsorbent in 100 parts of 15% sodium hydroxide solution, stirring in an ice water bath at 3 ℃, sequentially adding 15 parts of chloroacetic acid and 2.5 parts of ethylenediamine, continuously stirring for 50min, heating to 15 ℃, and stirring for 1 h;
adding 1 part of 30% sodium hydroxide solution in batches each time, adding the next batch after the phenolphthalein indicator does not show alkalinity after each addition, keeping the reactant at room temperature for 12 hours, heating to 85 ℃, adding 200 parts of deionized water, standing for 30 minutes, and naturally cooling to room temperature;
and (9) adding a 5% hydrochloric acid solution, soaking for 12h, washing with deionized water until the supernatant is neutral, and drying in a 60 ℃ oven to obtain the high-density porous carbon fiber adsorbent.
Example 5
A preparation method of a high-density porous carbon fiber adsorbent comprises the following steps:
opening the graphite felt leftover materials by using an opener to obtain graphite fibers;
step (2), a layer of graphite fiber is flatly laid, a layer of phenolic resin powder is covered, the graphite fiber and the phenolic resin powder are layered, and the modified graphite felt leftover material and the phenolic resin powder are in the following mass ratio: 50: 60; the number of layers of the modified graphite felt leftover material and the phenolic resin powder is 6 in total;
step (3), blank forming: drying and molding the laid materials at the pressure of 40MPa and the temperature of 300 ℃;
step (4), carbonization and activation: under the nitrogen atmosphere, carrying out high-temperature carbonization and activation to obtain the carbon fiber adsorbent, wherein the high-temperature carbonization conditions are as follows: 30min at 1000 ℃;
and (5) electrolyzing alkali liquor: the mixed solution of ammonium bicarbonate and p-phenylenediamine is used as electrolyte to electrolyze the surface of the activated carbon fiber adsorbent, wherein the current density is 0.9A/100cm2(ii) a The retention time is 14S; the electrolyte concentration is 4% ammonium bicarbonate and 0.9% p-phenylenediamine solution; the electrolysis temperature is 25 ℃;
and (6) cleaning: nitrogen bubbling cleaning is carried out in a water washing tank, the carbon fiber adsorbent after electrolysis is washed until the conductivity of effluent is less than or equal to 90us/cm, and the carbon fiber adsorbent is taken out and dried to obtain porous carbon fiber adsorbent;
soaking 9 parts of porous carbon fiber adsorbent in 100 parts of 15% sodium hydroxide solution, stirring in an ice water bath at 4 ℃, sequentially adding 15 parts of chloroacetic acid and 3 parts of ethylenediamine, continuously stirring for 50min, heating to 15 ℃, and stirring for 1 h;
adding 1 part of 30% sodium hydroxide solution in batches each time, adding the next batch after the phenolphthalein indicator does not show alkalinity after each addition, keeping the reactant at room temperature for 12 hours, heating to 85 ℃, adding 200 parts of deionized water, standing for 30 minutes, and naturally cooling to room temperature;
and (9) adding a 5% hydrochloric acid solution, soaking for 12h, washing with deionized water until the supernatant is neutral, and drying in a 60 ℃ oven to obtain the high-density porous carbon fiber adsorbent.
Example 6
A preparation method of a high-density porous carbon fiber adsorbent comprises the following steps:
opening the graphite felt leftover materials by using an opener to obtain graphite fibers;
step (2), a layer of graphite fiber is flatly laid, a layer of phenolic resin powder is covered, the graphite fiber and the phenolic resin powder are layered, and the modified graphite felt leftover material and the phenolic resin powder are in the following mass ratio: 60: 40; the number of layers of the modified graphite felt leftover material and the phenolic resin powder is 6 in total;
step (3), blank forming: drying and molding the laid materials at the pressure of 40MPa and the temperature of 300 ℃;
step (4), carbonization and activation: under the nitrogen atmosphere, carrying out high-temperature carbonization and activation to obtain the carbon fiber adsorbent, wherein the high-temperature carbonization conditions are as follows: 1100 ℃ for 60 min;
and (5) electrolyzing alkali liquor: the mixed solution of ammonium bicarbonate and p-phenylenediamine is used as electrolyte to electrolyze the surface of the activated carbon fiber adsorbent, wherein the current density is 0.9A/100cm2(ii) a The retention time is 15S; the electrolyte concentration is 5% ammonium bicarbonate and 1% p-phenylene-bisAn amine solution; the electrolysis temperature is 25 ℃;
and (6) cleaning: nitrogen bubbling cleaning is carried out in a water washing tank, the carbon fiber adsorbent after electrolysis is washed until the conductivity of effluent is less than or equal to 90us/cm, and the carbon fiber adsorbent is taken out and dried to obtain porous carbon fiber adsorbent;
soaking 10 parts of porous carbon fiber adsorbent in 100 parts of 15% sodium hydroxide solution, stirring in an ice water bath at 4 ℃, sequentially adding 15 parts of chloroacetic acid and 3 parts of ethylenediamine, continuously stirring for 50min, heating to 15 ℃, and stirring for 1 h;
adding 1 part of 30% sodium hydroxide solution in batches each time, adding the next batch after the phenolphthalein indicator does not show alkalinity after each addition, keeping the reactant at room temperature for 12 hours, heating to 85 ℃, adding 200 parts of deionized water, standing for 30 minutes, and naturally cooling to room temperature;
and (9) adding a 5% hydrochloric acid solution, soaking for 12h, washing with deionized water until the supernatant is neutral, and drying in a 60 ℃ oven to obtain the high-density porous carbon fiber adsorbent.
Example 7
A preparation method of a high-density porous carbon fiber adsorbent comprises the following steps:
opening the graphite felt leftover materials by using an opener to obtain graphite fibers;
step (2), a layer of graphite fiber is flatly laid, a layer of phenolic resin powder is covered, the graphite fiber and the phenolic resin powder are layered, and the modified graphite felt leftover material and the phenolic resin powder are in the following mass ratio: 40: 60; the number of layers of the modified graphite felt leftover material and the phenolic resin powder is 4 in total;
step (3), blank forming: drying and molding the laid materials at the pressure of 10MPa and the temperature of 300 ℃;
step (4), carbonization and activation: carbonizing and activating at low temperature in nitrogen atmosphere to obtain carbon fiber adsorbent, wherein the low-temperature carbonization condition is 350 ℃ for 60 min;
and (5) electrolyzing alkali liquor: taking the mixed solution of ammonium bicarbonate and p-phenylenediamine as electrolyte,electrolyzing the activated carbon fiber adsorbent surface, wherein the current density is 0.7A/100cm2(ii) a The retention time is 10S; the electrolyte concentration is 2% ammonium bicarbonate and 0.5% p-phenylenediamine solution; the electrolysis temperature is 25 ℃;
and (6) cleaning: nitrogen bubbling cleaning is carried out in a water washing tank, the carbon fiber adsorbent after electrolysis is washed until the conductivity of effluent is less than or equal to 90us/cm, and the carbon fiber adsorbent is taken out and dried to obtain porous carbon fiber adsorbent;
soaking 5 parts of porous carbon fiber adsorbent in 100 parts of 15% sodium hydroxide solution, stirring in an ice water bath at 0 ℃, sequentially adding 15 parts of chloroacetic acid and 2 parts of ethylenediamine, continuously stirring for 50min, heating to 15 ℃, and stirring for 1 h;
adding 1 part of 30% sodium hydroxide solution in batches each time, adding the next batch after the phenolphthalein indicator does not show alkalinity after each addition, keeping the reactant at room temperature for 12 hours, heating to 85 ℃, adding 200 parts of deionized water, standing for 30 minutes, and naturally cooling to room temperature;
and (9) adding a 5% hydrochloric acid solution, soaking for 12h, washing with deionized water until the supernatant is neutral, and drying in a 60 ℃ oven to obtain the high-density porous carbon fiber adsorbent.
Example 8
A preparation method of a high-density porous carbon fiber adsorbent comprises the following steps:
opening the graphite felt leftover materials by using an opener to obtain graphite fibers;
step (2), a layer of graphite fiber is flatly laid, a layer of phenolic resin powder is covered, the graphite fiber and the phenolic resin powder are layered, and the modified graphite felt leftover material and the phenolic resin powder are in the following mass ratio: 40: 50; the number of layers of the modified graphite felt leftover material and the phenolic resin powder is 6 in total;
step (2), blank forming: drying and molding the laid materials at the pressure of 20MPa and the temperature of 150 ℃;
step (3), carbonization and activation: carbonizing and activating at low temperature in nitrogen atmosphere to obtain carbon fiber adsorbent, wherein the low-temperature carbonization condition is 400 ℃ and 50 min;
and (5) electrolyzing alkali liquor: the mixed solution of ammonium bicarbonate and p-phenylenediamine is used as electrolyte to electrolyze the surface of the activated carbon fiber adsorbent, wherein the current density is 0.7A/100cm2(ii) a The retention time is 11S; the electrolyte concentration is 3% ammonium bicarbonate and 0.6% p-phenylenediamine solution; the electrolysis temperature is 25 ℃;
and (6) cleaning: nitrogen bubbling cleaning is carried out in a water washing tank, the carbon fiber adsorbent after electrolysis is washed until the conductivity of effluent is less than or equal to 90us/cm, and the carbon fiber adsorbent is taken out and dried to obtain porous carbon fiber adsorbent;
step (7) soaking 6 parts of porous carbon fiber adsorbent in 100 parts of 15% sodium hydroxide solution, stirring in an ice water bath at 1 ℃, sequentially adding 15 parts of chloroacetic acid and 2.5 parts of ethylenediamine, continuously stirring for 50min, heating to 15 ℃, and stirring for 1 h;
adding 1 part of 30% sodium hydroxide solution in batches each time, adding the next batch after the phenolphthalein indicator does not show alkalinity after each addition, keeping the reactant at room temperature for 12 hours, heating to 85 ℃, adding 200 parts of deionized water, standing for 30 minutes, and naturally cooling to room temperature;
and (9) adding a 5% hydrochloric acid solution, soaking for 12h, washing with deionized water until the supernatant is neutral, and drying in a 60 ℃ oven to obtain the high-density porous carbon fiber adsorbent.
Example 9
A preparation method of a high-density porous carbon fiber adsorbent comprises the following steps:
opening the graphite felt leftover materials by using an opener to obtain graphite fibers;
step (2), a layer of graphite fiber is flatly laid, a layer of phenolic resin powder is covered, the graphite fiber and the phenolic resin powder are layered, and the modified graphite felt leftover material and the phenolic resin powder are in the following mass ratio: 40: 40; the number of layers of the modified graphite felt leftover material and the phenolic resin powder is 6 in total;
step (2), blank forming: drying and molding the laid materials at the pressure of 30MPa and the temperature of 200 ℃;
step (3), carbonization and activation: carbonizing and activating at low temperature in nitrogen atmosphere to obtain carbon fiber adsorbent, wherein the low-temperature carbonization condition is 450 ℃ and 40 min; and (5) electrolyzing alkali liquor: the mixed solution of ammonium bicarbonate and p-phenylenediamine is used as electrolyte to electrolyze the surface of the activated carbon fiber adsorbent, wherein the current density is 0.8A/100cm2(ii) a The retention time is 12S; the electrolyte concentration is 3% ammonium bicarbonate and 0.7% p-phenylenediamine solution; the electrolysis temperature is 25 ℃;
and (6) cleaning: nitrogen bubbling cleaning is carried out in a water washing tank, the carbon fiber adsorbent after electrolysis is washed until the conductivity of effluent is less than or equal to 90us/cm, and the carbon fiber adsorbent is taken out and dried to obtain porous carbon fiber adsorbent;
step (7), soaking 7 parts of porous carbon fiber adsorbent in 100 parts of 15% sodium hydroxide solution, stirring in an ice-water bath at 2 ℃, sequentially adding 15 parts of chloroacetic acid and 2.5 parts of ethylenediamine, continuously stirring for 50min, heating to 15 ℃, and stirring for 1 h;
adding 1 part of 30% sodium hydroxide solution in batches each time, adding the next batch after the phenolphthalein indicator does not show alkalinity after each addition, keeping the reactant at room temperature for 12 hours, heating to 85 ℃, adding 200 parts of deionized water, standing for 30 minutes, and naturally cooling to room temperature;
and (9) adding a 5% hydrochloric acid solution, soaking for 12h, washing with deionized water until the supernatant is neutral, and drying in a 60 ℃ oven to obtain the high-density porous carbon fiber adsorbent.
Example 10
A preparation method of a high-density porous carbon fiber adsorbent comprises the following steps:
opening the graphite felt leftover materials by using an opener to obtain graphite fibers;
step (2), a layer of graphite fiber is flatly laid, a layer of phenolic resin powder is covered, the graphite fiber and the phenolic resin powder are layered, and the modified graphite felt leftover material and the phenolic resin powder are in the following mass ratio: 50: 40; the number of layers of the modified graphite felt leftover material and the phenolic resin powder is 6 in total;
step (3), blank forming: drying and molding the laid materials at the pressure of 30MPa and the temperature of 200 ℃;
step (4), carbonization and activation: carbonizing and activating at low temperature in nitrogen atmosphere to obtain carbon fiber adsorbent, wherein the low-temperature carbonization condition is 500 ℃ for 30 min;
and (5) electrolyzing alkali liquor: the mixed solution of ammonium bicarbonate and p-phenylenediamine is used as electrolyte to electrolyze the surface of the activated carbon fiber adsorbent, wherein the current density is 0.8A/100cm2(ii) a The retention time is 13S; the electrolyte concentration is 3% ammonium bicarbonate and 0.8% p-phenylenediamine solution; the electrolysis temperature is 25 ℃;
and (6) cleaning: nitrogen bubbling cleaning is carried out in a water washing tank, the carbon fiber adsorbent after electrolysis is washed until the conductivity of effluent is less than or equal to 90us/cm, and the carbon fiber adsorbent is taken out and dried to obtain porous carbon fiber adsorbent;
step (7), soaking 8 parts of porous carbon fiber adsorbent in 100 parts of 15% sodium hydroxide solution, stirring in an ice water bath at 3 ℃, sequentially adding 15 parts of chloroacetic acid and 2.5 parts of ethylenediamine, continuously stirring for 50min, heating to 15 ℃, and stirring for 1 h;
adding 1 part of 30% sodium hydroxide solution in batches each time, adding the next batch after the phenolphthalein indicator does not show alkalinity after each addition, keeping the reactant at room temperature for 12 hours, heating to 85 ℃, adding 200 parts of deionized water, standing for 30 minutes, and naturally cooling to room temperature;
and (9) adding a 5% hydrochloric acid solution, soaking for 12h, washing with deionized water until the supernatant is neutral, and drying in a 60 ℃ oven to obtain the high-density porous carbon fiber adsorbent.
Example 11
A preparation method of a high-density porous carbon fiber adsorbent comprises the following steps:
opening the graphite felt leftover materials by using an opener to obtain graphite fibers;
step (2), a layer of graphite fiber is flatly laid, a layer of phenolic resin powder is covered, the graphite fiber and the phenolic resin powder are layered, and the modified graphite felt leftover material and the phenolic resin powder are in the following mass ratio: 50: 60; the number of layers of the modified graphite felt leftover material and the phenolic resin powder is 6 in total;
step (3), blank forming: drying and molding the laid materials at the pressure of 40MPa and the temperature of 300 ℃;
step (4), carbonization and activation: carbonizing and activating at low temperature in nitrogen atmosphere to obtain carbon fiber adsorbent, wherein the low-temperature carbonization condition is 600 ℃ for 25 min;
and (5) electrolyzing alkali liquor: the mixed solution of ammonium bicarbonate and p-phenylenediamine is used as electrolyte to electrolyze the surface of the activated carbon fiber adsorbent, wherein the current density is 0.9A/100cm2(ii) a The retention time is 14S; the electrolyte concentration is 4% ammonium bicarbonate and 0.9% p-phenylenediamine solution; the electrolysis temperature is 25 ℃;
and (6) cleaning: nitrogen bubbling cleaning is carried out in a water washing tank, the carbon fiber adsorbent after electrolysis is washed until the conductivity of effluent is less than or equal to 90us/cm, and the carbon fiber adsorbent is taken out and dried to obtain porous carbon fiber adsorbent;
soaking 9 parts of porous carbon fiber adsorbent in 100 parts of 15% sodium hydroxide solution, stirring in an ice water bath at 4 ℃, sequentially adding 15 parts of chloroacetic acid and 3 parts of ethylenediamine, continuously stirring for 50min, heating to 15 ℃, and stirring for 1 h;
adding 1 part of 30% sodium hydroxide solution in batches each time, adding the next batch after the phenolphthalein indicator does not show alkalinity after each addition, keeping the reactant at room temperature for 12 hours, heating to 85 ℃, adding 200 parts of deionized water, standing for 30 minutes, and naturally cooling to room temperature;
and (9) adding a 5% hydrochloric acid solution, soaking for 12h, washing with deionized water until the supernatant is neutral, and drying in a 60 ℃ oven to obtain the high-density porous carbon fiber adsorbent.
Example 12
A preparation method of a high-density porous carbon fiber adsorbent comprises the following steps:
opening the graphite felt leftover materials by using an opener to obtain graphite fibers;
step (2), a layer of graphite fiber is flatly laid, a layer of phenolic resin powder is covered, the graphite fiber and the phenolic resin powder are layered, and the modified graphite felt leftover material and the phenolic resin powder are in the following mass ratio: 60: 40; the number of layers of the modified graphite felt leftover material and the phenolic resin powder is 6 in total;
step (3), blank forming: drying and molding the laid materials at the pressure of 40MPa and the temperature of 300 ℃;
step (4), carbonization and activation: carbonizing and activating at low temperature in nitrogen atmosphere to obtain carbon fiber adsorbent, wherein the low-temperature carbonization condition is 650 ℃ for 20 min;
and (5) electrolyzing alkali liquor: the mixed solution of ammonium bicarbonate and p-phenylenediamine is used as electrolyte to electrolyze the surface of the activated carbon fiber adsorbent, wherein the current density is 0.9A/100cm2(ii) a The retention time is 15S; the electrolyte concentration is 5% ammonium bicarbonate and 1% p-phenylenediamine solution; the electrolysis temperature is 25 ℃;
and (6) cleaning: nitrogen bubbling cleaning is carried out in a water washing tank, the carbon fiber adsorbent after electrolysis is washed until the conductivity of effluent is less than or equal to 90us/cm, and the carbon fiber adsorbent is taken out and dried to obtain porous carbon fiber adsorbent;
soaking 10 parts of porous carbon fiber adsorbent in 100 parts of 15% sodium hydroxide solution, stirring in an ice water bath at 4 ℃, sequentially adding 15 parts of chloroacetic acid and 3 parts of ethylenediamine, continuously stirring for 50min, heating to 15 ℃, and stirring for 1 h;
adding 1 part of 30% sodium hydroxide solution in batches each time, adding the next batch after the phenolphthalein indicator does not show alkalinity after each addition, keeping the reactant at room temperature for 12 hours, heating to 85 ℃, adding 200 parts of deionized water, standing for 30 minutes, and naturally cooling to room temperature;
and (9) adding a 5% hydrochloric acid solution, soaking for 12h, washing with deionized water until the supernatant is neutral, and drying in a 60 ℃ oven to obtain the high-density porous carbon fiber adsorbent.
20mL of Pb with the mass concentration of 10mg/L is taken2+The solution was placed in a series of 50mL centrifuge tubes and the pH adjusted to 4.0-6.0 with 0.1mol/L HCl and NaOH solutions. Weighing 0.5g of each example, respectively placing the examples in the solutions with different pH values, shaking the solutions in a constant temperature shaking box at 25 ℃ for 15h at the rotating speed of 125r/min, and measuring Pb in the adsorbed solutions by using FAAS2+The content of (a). The results are shown in Table 1.
TABLE 1 different examples and pH vs. Pb2+Amount of adsorption of (unit: mg/g)
At initial Pb2+、Cr2+、Cu2+Taking 0.5g of each example when the mass concentration is 10mg/L, the pH =5.00, the adsorption time is 25h and the temperature is 30 ℃, shaking for 15h at 25 ℃ in a constant temperature shaking box at the rotating speed of 125r/min, and measuring the maximum adsorption capacity to different heavy metal solutions. The results are shown in Table 2.
TABLE 2 adsorption amounts (unit: mg/g) of different kinds of heavy metal ions
As can be seen from Table 2, when Pb is present in the solution2+、Cr2+And Cu2+When various heavy metal ions exist, the material of the invention not only can be used for treating Pb2+Has better adsorption effect and better adsorption effect on other different heavy metals, and the adsorption affinity of the heavy metal is expressed as Pb2+＞Cu2+＞Cr2+。
Claims (6)
1. A preparation method of a high-density porous carbon fiber adsorbent is characterized by comprising the following steps: the method comprises the following steps:
opening the graphite felt leftover materials by using an opener to obtain graphite fibers;
step (2), a layer of graphite fiber is flatly laid, a layer of phenolic resin powder is covered, and the graphite fiber and the phenolic resin powder are layered;
step (3), blank forming: drying and forming the laid materials;
step (4), carbonization and activation: carbonizing and activating the mixture in a nitrogen atmosphere to obtain a carbon fiber adsorbent;
and (5) electrolyzing alkali liquor: taking a mixed solution of ammonium bicarbonate and p-phenylenediamine as an electrolyte, and electrolyzing the surface of the activated carbon fiber adsorbent;
and (6) cleaning: nitrogen bubbling cleaning is carried out in a water washing tank, the carbon fiber adsorbent after electrolysis is washed until the conductivity of effluent is less than or equal to 90us/cm, and the carbon fiber adsorbent is taken out and dried to obtain porous carbon fiber adsorbent;
soaking 5-10 parts of porous carbon fiber adsorbent in 100 parts of 15% sodium hydroxide solution, stirring in an ice water bath at 0-4 ℃, sequentially adding 15 parts of chloroacetic acid and 2-3 parts of ethylenediamine, continuously stirring for 50min, heating to 15 ℃, and stirring for 1 h;
adding 1 part of 30% sodium hydroxide solution in batches each time, adding the next batch after the phenolphthalein indicator does not show alkalinity after each addition, keeping the reactant at room temperature for 12 hours, heating to 85 ℃, adding 200 parts of deionized water, standing for 30 minutes, and naturally cooling to room temperature;
and (9) adding a 5% hydrochloric acid solution, soaking for 12h, washing with deionized water until the supernatant is neutral, and drying in a 60 ℃ oven to obtain the high-density porous carbon fiber adsorbent.
2. The method for preparing a high-density porous carbon fiber adsorbent according to claim 1, characterized in that: the mass ratio of the layer of graphite fiber to the layer of phenolic resin powder in the step (2) is as follows: (40-60) and (60-40).
3. The method for preparing a high-density porous carbon fiber adsorbent according to claim 1, characterized in that: the number of layers of the graphite fibers and the phenolic resin powder in the step (2) is 4-8.
4. The method for preparing a high-density porous carbon fiber adsorbent according to claim 1, characterized in that: the drying and forming pressure in the step (3) is 10-40 MPa, and the temperature is 100-300 ℃.
5. The method for preparing a high-density porous carbon fiber adsorbent according to claim 1, characterized in that: the activation in the step (4) comprises high-temperature carbonization and low-temperature carbonization, and the high-temperature carbonization conditions are as follows: 700-1100 ℃ for 30-90 min; the low-temperature carbonization condition is 350-650 ℃ and 20-60 min.
6. The method for preparing a high-density porous carbon fiber adsorbent according to claim 1, characterized in that: the current density in the step (5) is 0.7-0.9A/100 cm2(ii) a The retention time is 10-15 s; the electrolyte concentration is 2% -5% ammonium bicarbonate and 0.5% -1% p-phenylenediamine solution; the electrolysis temperature was 25 ℃.
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