CN112588267A - Composite porous carbon capable of efficiently adsorbing mercury and preparation method thereof - Google Patents

Composite porous carbon capable of efficiently adsorbing mercury and preparation method thereof Download PDF

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CN112588267A
CN112588267A CN202011345250.0A CN202011345250A CN112588267A CN 112588267 A CN112588267 A CN 112588267A CN 202011345250 A CN202011345250 A CN 202011345250A CN 112588267 A CN112588267 A CN 112588267A
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porous carbon
bagasse
preparation
composite porous
reaction
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CN112588267B (en
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马年方
李锦荣
陈骏佳
曾建
谭文兴
王庆福
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Institute of Bioengineering of Guangdong Academy of Sciences
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Institute of Bioengineering of Guangdong Academy of Sciences
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Abstract

The invention discloses a preparation method of composite porous carbon for efficiently adsorbing mercury, which comprises the steps of preparation of bagasse-based porous carbon, preparation of carboxylated porous carbon, preparation of aminated modified bagasse and preparation of composite porous carbon.

Description

Composite porous carbon capable of efficiently adsorbing mercury and preparation method thereof
Technical Field
The invention relates to the technical field of porous material preparation, in particular to aminated bagasse composite porous carbon capable of quickly adsorbing mercury with high capacity and a preparation method thereof.
Background
Heavy metal ions, particularly mercury and compounds thereof, are highly toxic and highly volatile neurotoxins, have nondegradable property, can enter a human body through a food chain even at a low concentration, and are continuously enriched in the human body, so that the health of the human body is finally affected, and the removal of the heavy metal mercury in the environment is concerned. In recent years, the problem of environmental pollution caused by mercury and its compounds has become increasingly serious. Although the existing emission requirements are below 50ppb, the existing mercury removal process cannot meet the emission requirements, and if the removal of low-concentration and trace heavy metal mercury in ultra-clean high-purity reagents is considered, the requirement on ultra-low concentration is higher, because the lower the concentration is, the more difficult the removal is.
At present, the treatment methods of mercury-containing solution are many, such as chemical precipitation method, electrolytic method, coagulation method, activated carbon adsorption method, reduction method and electrolytic method, but the common defect of the methods is that the mercury with low concentration is difficult to remove. The chelate fiber is ion adsorption fiber containing special functional groups, and the chelate fiber adsorbs metal ions by using the special groups on the fiber, so that the chelate fiber has the advantages of high adsorption capacity, good selectivity, easy elution, easy regeneration and the like, and most importantly, the chelate fiber can also effectively adsorb and remove low-concentration mercury to reach the safety standard of drinking water.
The ultra-clean high-purity reagent is a key process chemical for etching a super-large scale integrated circuit, is mainly used for chip cleaning corrosion and silicon wafer cleaning, and has very important influence on the yield, the electrical property and the reliability of the integrated circuit. The removal of low concentration or trace heavy metal ions such as mercury in ultra-clean high purity reagents has been a difficult problem. The amine modified fiber material has higher adsorption capacity, but the adsorption speed needs to be further improved. Among a plurality of adsorbents, the porous carbon material has the advantages of three-dimensionally communicated pore channels, high specific surface area, high mechanical strength and the like, and particularly, the amine modified fiber material can quickly adsorb heavy metal ions through huge specific surface area and pore adsorption effect. In the industrial process of adsorption treatment, in order to meet the requirements of industrialization and high-efficiency treatment, on one hand, the contact time of the reagent and the adsorption material needs to be further shortened, which needs to improve the adsorption speed, and on the other hand, the material needs to have high adsorption capacity in order to reduce the frequency of replacing the adsorption material or the adsorption column. Therefore, the development of a novel composite porous carbon adsorption material with rapid and high capacity for mercury adsorption is urgently needed.
Disclosure of Invention
In view of the above, the invention provides a preparation method of composite porous carbon capable of efficiently adsorbing mercury, which comprises the steps of preparing carboxylated porous carbon with a proper pore size by utilizing a high-efficiency hierarchical porous structure formed by naturally evolving bagasse in a growth process through carbonization activation, surface activation and carboxylation modification, preparing modified bagasse rich in amino groups by performing surface activation and grafting modification on the bagasse, and then reacting the modified bagasse with the modified bagasse to prepare an aminated bagasse composite porous carbon material with rapid adsorption capacity and high capacity for mercury ions.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of composite porous carbon for efficiently adsorbing mercury comprises the following steps:
(1) preparation of bagasse-based porous carbon: carbonizing bagasse to obtain carbonized bagasse, then mixing alkali and the carbonized bagasse by using alkali as an activating agent, calcining, activating, washing and drying to obtain porous carbon;
(2) preparation of carboxylated porous carbon: reacting the porous carbon with concentrated nitric acid with the mass concentration of 10-12% for 1-5h at the temperature of 40-70 ℃, washing with water, and drying to obtain carboxylated porous carbon for later use;
(3) preparing aminated modified bagasse: adding pretreated bagasse into an activated monomer aqueous solution for a grafting reaction, introducing nitrogen, heating, adding Mohr's salt, hydrogen peroxide and acetic acid as catalysts in sequence after the reaction temperature is reached, stirring for reaction, washing and cooking a reaction product to remove a homopolymer, washing with deionized water, performing suction filtration, and drying to obtain grafted bagasse;
adding amine monomers into the grafted bagasse to perform amination reaction, and after the reaction is finished, washing, filtering and drying to obtain aminated modified bagasse for later use;
(4) preparation of composite porous carbon: and (3) adding ultrapure water into the carboxylated porous carbon prepared in the step (2) to prepare suspension, adding NHS into the suspension, performing ultrasonic treatment to activate carboxyl on the carboxylated porous carbon, sequentially adding the aminated modified bagasse and EDC prepared in the step (3), reacting at room temperature, performing suction filtration, and drying to obtain the composite porous carbon.
It should be noted that the key to step (4) is that NHS is added first, NHS cannot be added simultaneously with EDC, and the reaction is started by adding aminated modified bagasse and then adding EDC after stirring uniformly.
Preferably, in the preparation method of the composite porous carbon for efficiently adsorbing mercury, the carbonization temperature in the step (1) is 400-700 ℃, preferably 500-650 ℃, and more preferably 500 ℃;
the alkali is an alkaline inorganic substance, preferably potassium hydroxide;
the calcination temperature is 600-900 ℃, preferably 600-800 ℃, and more preferably 600 ℃.
Preferably, in the above preparation method of the composite porous carbon for efficiently adsorbing mercury, the reaction condition in the step (2) is reaction at 60 ℃ for 3 h.
Preferably, in the above preparation method of composite porous carbon for efficiently adsorbing mercury, the pretreatment step in step (3) is: crushing and screening bagasse, soaking in 2-20% alkali solution for 1-24 hr, and drying.
The beneficial effects of the above technical scheme are: most of hemicellulose and lignin in the bagasse can be removed by alkali liquor and activated bagasse surface groups.
Preferably, in the above preparation method of composite porous carbon for efficiently adsorbing mercury, the activated monomer in step (3) is any one of acrylamide, acrylonitrile and glycidyl methacrylate, and the concentration of the activated monomer aqueous solution is 6% -18%, and the volume of the activated monomer aqueous solution is 100-.
Preferably, in the preparation method of the composite porous carbon for efficiently adsorbing mercury, the reaction temperature of the grafting reaction in the step (3) is 40-80 ℃, and the reaction time is 1-6 h.
Preferably, in the preparation method of the composite porous carbon capable of efficiently adsorbing mercury, in step (3), per 100ml of the active monomer aqueous solution, the addition amount of the Mohr salt is 0.02-0.1g, the addition amount of the hydrogen peroxide is 0.2-1ml, and the volume percentage of the acetic acid is 0.2-1%, and further preferably, per 100ml of the active monomer aqueous solution, the addition amount of the Mohr salt is 0.06g, the addition amount of the hydrogen peroxide is 0.5ml, and the volume percentage of the acetic acid is 0.2-1%.
Preferably, in the preparation method of the composite porous carbon capable of efficiently adsorbing mercury, the amine monomer in the step (3) is any one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and polyethylene polyamine.
Preferably, in the preparation method of the composite porous carbon for efficiently adsorbing mercury, the reaction temperature of the amination reaction in the step (3) is 110-150 ℃, and the reaction time is 1-5 h.
Preferably, in the preparation method of the composite porous carbon for efficiently adsorbing mercury, the mass ratio of the carboxylated modified porous carbon, the NHS and the EDC in the step (4) is 20:1: 2; the mass ratio of the aminated modified bagasse to the carboxylated modified porous carbon is 1:2-2: 1.
The beneficial effects of the above technical scheme are: the addition amounts of the carboxylated modified porous carbon, the NHS, the EDC and the aminated modified bagasse are obtained after a large number of tests prove that if the addition amounts exceed the ranges, the adsorption capacity of the finally obtained composite porous carbon material to mercury ions is reduced, and the adsorption equilibrium time is prolonged.
Preferably, in the preparation method of the composite porous carbon for efficiently adsorbing mercury, the ultrasonic time in the step (4) is 20-40min, and the room-temperature reaction time is 1-3 h.
The invention also discloses the composite porous carbon for efficiently adsorbing mercury, which is prepared by the method.
According to the technical scheme, compared with the prior art, the invention discloses and provides the composite porous carbon for efficiently adsorbing mercury and the preparation method thereof, and the composite porous carbon has the following advantages:
(1) according to the invention, the bagasse is subjected to a high-efficiency hierarchical porous structure formed by natural evolution in the growth process, the naturally-graded porous structure and the air passage of the bagasse are still remained after carbonization and activation, and the prepared porous carbon has a plurality of micropores, mesopores and intercommunicates on the surface and inside, and the intercommunicates are beneficial to mass transfer and diffusion of adsorbates and rapid adsorption of mercury ions.
(2) According to the invention, the aminated modified bagasse is compounded with the porous carbon, the porous carbon can quickly attract and adsorb mercury ions on the surface of the porous carbon, the aminated modified bagasse with high amino content has enough effective amino groups to provide high adsorption capacity, the mercury is efficiently adsorbed and removed without dead angles by utilizing the synergistic effect generated by the physical adsorption and the covalent combination of the physical adsorption and the chemical adsorption of organic amine, and the mercury adsorption and removal effect of the bagasse composite porous carbon on the mercury is greatly improved.
(3) The method selects the bagasse as the raw material, has low cost, widens the source of the raw material for preparing the high-performance porous carbon, and realizes the effective utilization of resources.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is the adsorption isotherm of Aminated Bagasse (AB), Porous Carbon (PC) and aminated bagasse composite porous carbon (AB & PC) of example 1 for mercury;
FIG. 2 is a graph of the adsorption kinetics of Aminated Bagasse (AB), Porous Carbon (PC) and aminated bagasse composite porous carbon (AB & PC) of example 1;
FIG. 3 is a scanning electron microscope image of the aminated bagasse composite porous carbon prepared in example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
1g of bagasse is put into a carbonization furnace, carbonized for 3 hours at 500 ℃, uniformly mixed with 4g of KOH to be used as an activating agent, calcined and activated at 600 ℃, washed and dried. Adding 12% concentrated nitric acid into the obtained porous carbon, and reacting for 3h at 60 ℃ to obtain the carboxylated porous carbon.
Taking bagasse which is ground to have the grain size of 20 meshes, soaking the bagasse in a NaOH solution with the concentration of 5%, soaking for 24 hours, and filtering to dry after soaking; taking 10g of pretreated bagasse, adding the pretreated bagasse into 10mL of acrylamide aqueous solution, adding deionized water to 100mL, introducing nitrogen, heating, adding 0.05g of Mohr's salt into 0.6mL of hydrogen peroxide and 0.4mL of acetic acid in sequence after the reaction temperature is reached, and reacting for 5 hours at 50 ℃. Washing the reaction product with water, steaming in boiling water to remove homopolymer, washing with deionized water, filtering, and drying; and taking 10g of the grafted bagasse, adding diethylenetriamine into the grafted bagasse, reacting for 5 hours at the temperature of 120 ℃, washing, filtering and drying to obtain the aminated modified bagasse.
Preparing aminated modified bagasse composite porous carbon: taking 1g of carboxylated modified porous carbon, and adding ultrapure water to prepare suspension; adding 50mg of NHS, performing ultrasonic treatment for 30min to activate carboxyl on porous carbon, adding 2g of aminated modified bagasse into the suspension, adding 100mg of EDC, reacting at room temperature for 2h, washing with water, performing suction filtration, and drying to obtain the aminated modified bagasse composite porous carbon.
0.1g of aminated modified bagasse composite porous carbon prepared in the embodiment is added into a series of mercury ion solutions with different initial concentrations, the materials are placed into a shaking table to be oscillated for 12 hours, an intelligent mercury photometer is adopted to measure the concentration of the residual mercury ions, the adsorption capacity of the composite porous carbon material to the mercury ions can be calculated according to the adsorption isotherm, 1178.5mg/g of the adsorption capacity of the composite porous carbon material to the mercury ions can be obtained, and the time for reaching the adsorption balance can be known to be 10 minutes according to the kinetic adsorption curve.
Example 2
1g of bagasse is put into a carbonization furnace and carbonized for 1h at 700 ℃; taking out the porous carbon, uniformly stirring the porous carbon and 4g of KOH to be used as an activating agent, calcining and activating at 700 ℃, washing and drying, adding 12% concentrated nitric acid into the obtained porous carbon, and reacting for 5 hours at 40 ℃ to obtain the carboxylated porous carbon.
Taking bagasse which is ground to have the grain size of 20 meshes, soaking the bagasse in a NaOH solution with the concentration of 5%, soaking for 1h, and filtering to dry after soaking; taking 10g of pretreated bagasse, adding the pretreated bagasse into 6mL of acrylonitrile aqueous solution, adding deionized water to 100mL, introducing nitrogen, heating, adding 0.02g of Mohr's salt into 1.0mL of hydrogen peroxide and 1.0mL of acetic acid after the reaction temperature is reached, and reacting for 1h at 80 ℃. Washing the reaction product with water, steaming in boiling water to remove homopolymer, washing with deionized water, filtering, and drying; and taking 10g of the grafted bagasse, adding tetraethylenepentamine into the grafted bagasse, reacting for 2 hours at 140 ℃, washing with water, performing suction filtration, and drying to obtain the aminated modified bagasse.
Preparing aminated modified bagasse composite porous carbon: taking 2g of carboxylated modified porous carbon, and adding ultrapure water to prepare suspension; adding 100mg of NHS, performing ultrasonic treatment for 20min to activate carboxyl on porous carbon, adding 1g of aminated modified bagasse into the suspension, adding 200mg of EDC, and reacting at room temperature for 1 h. And washing, filtering and drying to obtain the aminated modified bagasse composite porous carbon.
0.1g of aminated modified bagasse composite porous carbon prepared in the embodiment is added into a series of mercury ion solutions with different initial concentrations, the materials are placed into a shaking table to be oscillated for 12 hours, an intelligent mercury photometer is adopted to measure the concentration of the residual mercury ions, the adsorption capacity of the composite porous carbon material to the mercury ions can be calculated according to the adsorption isotherm, 926.8mg/g of the adsorption capacity of the composite porous carbon material to the mercury ions can be obtained, and the time for reaching the adsorption balance can be known to be 12 minutes according to the kinetic adsorption curve.
Example 3
1g of bagasse is put into a carbonization furnace, carbonized for 2 hours at 600 ℃, uniformly mixed with 4g of KOH to be used as an activating agent, calcined and activated at 700 ℃, washed and dried. Adding 12% concentrated nitric acid into the obtained porous carbon, and reacting for 2h at 70 ℃ to obtain the carboxylated porous carbon.
Taking bagasse which is ground to have the grain size of 20 meshes, soaking the bagasse in NaOH solution with the concentration of 8% for 1 hour, and filtering the bagasse after soaking; taking 10g of pretreated bagasse, adding the pretreated bagasse into 18mL of glycidyl methacrylate aqueous solution, adding deionized water to 100mL, introducing nitrogen, heating, adding 1.0g of Mohr's salt into 1.0mL of hydrogen peroxide and 0.2mL of acetic acid in sequence after the reaction temperature is reached, and reacting for 5 hours at 40 ℃. Washing the reaction product with water, steaming in boiling water to remove homopolymer, washing with deionized water, filtering, and drying; and taking 10g of the grafted bagasse, adding diethylenetriamine into the grafted bagasse, reacting for 1h at 150 ℃, washing with water, filtering by suction, and drying to obtain the aminated modified bagasse.
Preparing aminated modified bagasse composite porous carbon: taking 1g of carboxylated modified porous carbon, and adding ultrapure water to prepare suspension; adding 50mg of NHS, performing ultrasonic treatment for 40min to activate carboxyl on porous carbon, adding 1g of aminated modified bagasse into the suspension, adding 100mg of EDC, and reacting at room temperature for 3 h. And washing, filtering and drying to obtain the aminated modified bagasse composite porous carbon.
0.1g of aminated modified bagasse composite porous carbon prepared in the embodiment is added into a series of mercury ion solutions with different initial concentrations, the materials are placed into a shaking table to be oscillated for 12 hours, an intelligent mercury photometer is adopted to measure the concentration of the residual mercury ions, the adsorption capacity of the composite porous carbon material to the mercury ions can be calculated according to the adsorption isotherm, 1045.5mg/g of the adsorption capacity of the composite porous carbon material to the mercury ions can be obtained, and the time for reaching the adsorption balance can be known to be 8 minutes according to the kinetic adsorption curve.
Comparative example 1 (porous carbon)
1g of bagasse is put into a carbonization furnace, carbonized for 3 hours at 500 ℃, uniformly mixed with 4g of KOH to be used as an activating agent, calcined and activated at 600 ℃, washed and dried. Adding 12% concentrated nitric acid into the obtained porous carbon, and reacting for 3h at 60 ℃ to obtain the carboxylated porous carbon.
Taking 0.1g of bagasse porous carbon prepared in the comparative example, adding the bagasse porous carbon into a series of mercury ion solutions with different initial concentrations, placing the bagasse porous carbon into a shaking table for oscillation for 12 hours, measuring the concentration of the residual mercury ions by using an intelligent mercury measuring instrument, calculating the adsorption capacity of the composite porous carbon material to the mercury ions according to the adsorption isotherm to obtain 441.9mg/g, and knowing the time for reaching adsorption balance according to the kinetic adsorption curve to be 5 min.
Comparative example 2 (aminated bagasse)
Taking bagasse which is ground to have the grain size of 20 meshes, soaking the bagasse in a NaOH solution with the concentration of 5%, soaking for 24 hours, and filtering to dry after soaking; taking 10g of pretreated bagasse, adding the pretreated bagasse into 10mL of acrylamide aqueous solution, adding deionized water to 100mL, introducing nitrogen, heating, adding 0.05g of Mohr's salt into 0.6mL of hydrogen peroxide and 0.4mL of acetic acid in sequence after the reaction temperature is reached, and reacting for 5 hours at 50 ℃. Washing the reaction product with water, steaming in boiling water to remove homopolymer, washing with deionized water, filtering, and drying; and taking 10g of the grafted bagasse, adding diethylenetriamine into the grafted bagasse, reacting for 5 hours at the temperature of 120 ℃, washing, filtering and drying to obtain the aminated modified bagasse.
Taking 0.1g of aminated modified bagasse prepared in the comparative example, adding the aminated modified bagasse into a series of mercury ion solutions with different initial concentrations, placing the materials into a shaking table for oscillation for 12 hours, measuring the concentration of the residual mercury ions by adopting an intelligent mercury measuring instrument, calculating the adsorption capacity of the composite porous carbon material to the mercury ions according to the adsorption isotherm to obtain 864.9mg/g, and knowing the time for reaching the adsorption balance according to the kinetic adsorption curve to be 30 min.
Comparative example 3 (two-stage amine modified porous carbon)
(1) Preparing bagasse-based hierarchical porous carbon: carbonizing bagasse at 500 deg.C, calcining and activating at 600 deg.C with KOH as activating agent (the KOH amount is 4 times of bagasse weight), and using HNO with concentration of 10% by mass3Washing the solution with distilled water to prepare hierarchical porous carbon;
(2) surface oxidation activation of bagasse-based hierarchical porous carbon: dissolving 10g of hierarchical porous carbon in 100ml of acetic acid solution with the concentration of 30% by mass fraction, and adding 2ml of composite oxidant to react for 3 hours at 50 ℃, wherein the composite oxidant comprises the following components: ammonium persulfate with the concentration of 20 percent by mass, sulfuric acid solution with the concentration of 10 percent by mass, and water as a solvent; and (4) washing, suction filtering and drying to obtain the oxygen-containing hierarchical porous carbon.
(3) Preparation of hyperbranched polyamidoamines: dissolving 100mL of triethylene tetramine in 100mL of methanol, pouring the mixture into a three-necked bottle, placing the three-necked bottle in an ice bath, slowly dropwise adding a mixed solution consisting of 59mL of methyl acrylate and 100mL of methanol, removing the methanol by rotary evaporation at 50 ℃ after dropwise adding, and then reacting for 24 hours at 100 ℃ to obtain the hyperbranched polyamide-amine.
(4) Preparing two-stage amine modified bagasse hierarchical porous carbon: adding 10g of the oxygen-containing porous carbon prepared in the step (2) into a polytetrafluoroethylene reactor filled with 100ml of hyperbranched polyamide-amine, sealing, reacting for 2 hours at 130 ℃, alternately washing cold water and hot water (cold water is tap water, hot water is water with the temperature of more than 80 ℃), filtering and drying; taking 10g of a dry sample, adding the dry sample into a polytetrafluoroethylene reactor filled with 100ml of triethylene tetramine, sealing, reacting for 1h at 140 ℃, washing a reaction product after the reaction is finished, boiling the reaction product in boiling water for 10min, washing the reaction product with deionized water, filtering, and drying.
Taking 0.1g of the two sections of amine modified porous carbon prepared in the comparative example, adding the two sections of amine modified porous carbon into a series of mercury ion solutions with different initial concentrations, placing the solutions into a shaking table for oscillation for 12 hours, measuring the concentration of the residual mercury ions by adopting an intelligent mercury measuring instrument, calculating according to an adsorption isotherm to obtain that the adsorption capacity of the composite porous carbon material to the mercury ions is 782.1.mg/g, and knowing that the time for reaching adsorption balance is 12min according to a kinetic adsorption curve.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. For the scheme disclosed by the embodiment, the scheme corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. The preparation method of the composite porous carbon for efficiently adsorbing mercury is characterized by comprising the following steps:
(1) preparation of bagasse-based porous carbon: carbonizing bagasse to obtain carbonized bagasse, then mixing alkali and the carbonized bagasse by using alkali as an activating agent, calcining, activating, washing and drying to obtain porous carbon;
(2) preparation of carboxylated porous carbon: reacting the porous carbon with concentrated nitric acid with the mass concentration of 10-12% for 1-5h at 40-70 ℃, washing with water, and drying to obtain carboxylated porous carbon for later use;
(3) preparing aminated modified bagasse: adding pretreated bagasse into an activated monomer aqueous solution for a grafting reaction, introducing nitrogen, heating, adding Mohr's salt, hydrogen peroxide and acetic acid as catalysts in sequence after the reaction temperature is reached, stirring for reaction, washing and cooking a reaction product to remove a homopolymer, washing with deionized water, performing suction filtration, and drying to obtain grafted bagasse;
adding amine monomers into the grafted bagasse to perform amination reaction, and after the reaction is finished, washing, filtering and drying to obtain aminated modified bagasse for later use;
(4) preparation of composite porous carbon: and (3) adding ultrapure water into the carboxylated porous carbon prepared in the step (2) to prepare suspension, adding NHS into the suspension, performing ultrasonic treatment to activate carboxyl on the carboxylated porous carbon, sequentially adding the aminated modified bagasse and EDC prepared in the step (3), reacting at room temperature, performing suction filtration, and drying to obtain the composite porous carbon.
2. The preparation method of the composite porous carbon for efficiently adsorbing mercury according to claim 1, wherein the pretreatment step in the step (3) is: crushing and screening bagasse, soaking in 2-20% alkali solution for 1-24 hr, and drying.
3. The preparation method of the composite porous carbon for efficiently adsorbing mercury according to claim 1, wherein the activated monomer in the step (3) is any one of acrylamide, acrylonitrile and glycidyl methacrylate, and the concentration of the aqueous solution of the activated monomer is 6% -18%.
4. The preparation method of the composite porous carbon for efficiently adsorbing mercury according to claim 1, wherein the reaction temperature of the grafting reaction in the step (3) is 40-80 ℃, and the reaction time is 1-6 h.
5. The preparation method of the composite porous carbon for efficiently adsorbing mercury according to claim 1, wherein in each 100ml of the active monomer aqueous solution in the step (3), the addition amount of the Mohr salt is 0.02-0.1g, the addition amount of the hydrogen peroxide is 0.2-1ml, and the volume percentage of the acetic acid is 0.2-1%.
6. The preparation method of the composite porous carbon capable of efficiently adsorbing mercury according to claim 1, wherein the amine monomer in the step (3) is any one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and polyethylene polyamine.
7. The preparation method of the composite porous carbon for efficiently adsorbing mercury according to claim 1, wherein the amination reaction in the step (3) is carried out at a temperature of 110 ℃ and 150 ℃ for 1-5 h.
8. The preparation method of the composite porous carbon for efficiently adsorbing mercury according to claim 1, characterized in that the mass ratio of the carboxylated modified porous carbon, the NHS and the EDC in the step (4) is 20:1: 2; the mass ratio of the aminated modified bagasse to the carboxylated modified porous carbon is 1:2-2: 1.
9. The preparation method of the composite porous carbon for efficiently adsorbing mercury according to claim 1, wherein the ultrasonic time in the step (4) is 20-40min, and the room-temperature reaction time is 1-3 h.
10. Composite porous carbon capable of efficiently adsorbing mercury prepared by the method of any one of claims 1 to 9.
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