• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention discloses a method for producing a porous composite carbon which adsorbs mercury efficiently, comprising producing bagasse-based porous carbon, producing carboxylated porous carbon, producing aminated modified bagasse, and producing porous composite carbon. On the one hand, the highly efficient tiered porous structure created by the natural development of bagasse during the growth process is used, then through carbonization activation, surface activation and carboxylation modification, carboxylated porous carbon with suitable pore size is produced. On the other hand, the modified bagasse having rich amine groups is produced by surface activation and graft modification of bagasse, and then the two react to produce the porous aminated bagasse composite carbon material, which has a quick adsorbing ability and a large capacity for mercury.
    公开号:BE1027994B1
    申请号:E20205913
    申请日:2020-12-14
    公开日:2021-08-10
    发明作者:Qingfu Wang；Junjia Chen；Nianfang Ma；Jinrong Li；Wenxing Tan；Jian Zeng
    申请人:Guangdong Academy Of Sciences Inst Of Bioengineering；
    IPC主号:
    专利说明:

    ; BE2020 / 5913 Porous composite carbon for efficient adsorbing of mercury and manufacturing process thereof
    TECHNICAL FIELD The present invention relates to the technical field of producing porous material, and more particularly, to a porous composite carbon of aminated bagasse which can adsorb mercury quickly and with high capacity, and a production method thereof.
    PRIOR ART Heavy metal ions, in particular mercury and its compounds, are highly toxic and highly volatile neurotoxins. They are not degradable and at low concentrations can enter the human body via the food chain and continuously accumulate in the human body, ultimately affecting human health, so that the removal of heavy metal mercury in the environment has attracted a lot of attention. In recent years, environmental pollution caused by mercury and its compounds has become increasingly serious. Although the current emission requirement is envisaged to be less than 50 ppb, the existing mercury removal process still cannot meet the emission requirement. When the removal of low concentration mercury and traces of heavy metals in the ultrapure and ultrapure reagent is taken into account, the requirement for an extremely low concentration is higher because the lower the concentration, the more difficult it is to remove.
    At present, there are many treatment methods for solutions containing mercury, such as chemical precipitation, electrolysis, coagulation, adsorption with activated carbon, reduction and electrolysis. However, a common disadvantage of these methods is that it is difficult to remove low concentration mercury. Heavy metal ion wastewater of low concentration can be treated with ion exchange and chelate adsorption. Among them, chelate fiber is an ion adsorption fiber that contains specific functional groups, while it uses the specific groups on the fiber to adsorb metal ions, and has advantages of high adsorption capacity, good selectivity, easy elution and regeneration, and so on. The most important thing is that it can effectively adsorb and remove even low concentration mercury while achieving the safety standard of drinking water.
    Ultra-pure and ultra-pure reagents are the most important process chemicals for large-scale etching of integrated circuits. They are mainly used for cleaning and corrosion of chips and for cleaning silicon wafers. Their purity has a very large influence on the yield, the electrical output and the
    ° BE2020 / 5913 Reliability of the integrated circuits. It has always been a focus to remove heavy metal ions such as mercury in low concentrations or traces in ultra-pure and ultra-pure reagents. Amine-modified fiber materials have a higher adsorption capacity, but the adsorption rate needs to be further improved. Among the many adsorbents, porous carbon materials have advantages of high specific surface area and high mechanical strength due to the three-dimensional connected channels. Amine-modified fiber materials in particular can quickly adsorb heavy metal ions due to a large specific surface area and a pore adsorption effect. In the industrialization of adsorption treatment, on the one hand, the contact time between the reagent and the adsorbent material should be further shortened in order to meet the requirements of industrialization and highly efficient processing, whereby the increased adsorption speed is necessary, on the other hand, a high adsorption capacity of the material is necessary to achieve the To reduce the frequency of replacing the adsorbent materials or adsorbent columns. Therefore, there is an urgent need to develop a new porous composite carbon adsorbent material for faster adsorption with high adsorbing capacity for mercury.
    SUMMARY OF THE PRESENT INVENTION In view of the above, the present invention provides a method for producing a porous composite carbon that adsorbs mercury efficiently. On the one hand, the highly efficient graded porous structure created by the natural development of bagasse during the growth process is used, then by carbonization activation, surface activation and carboxylation modification, carboxylated porous carbon with suitable pore size is produced. On the other hand, the modified bagasse having rich amine groups is produced by surface activation and graft modification of bagasse, and then the two react to produce the porous aminated bagasse composite carbon material which has a quick adsorbing ability and a large capacity for mercury. In order to achieve the above objects, the present invention adopts the following technical solutions: A method of producing porous composite carbon for efficiently adsorbing mercury, comprising the steps of: (1) producing bagasse-based porous carbon, the bagasse being carbonized and obtaining carbonized bagasse using alkali as an activator, the alkali being mixed with carbonized bagasse, calcined and activated, then washed and dried to obtain the porous carbon; (2) Manufacture of carboxylated porous carbon, the porous carbon with concentrated nitric acid in mass concentration of 10-12% at a temperature
    ° BE2020 / 5913 is reacted at 40 - 70 ° C for 1 - 5 hours, washing with water and drying, and then obtaining the carboxylated porous carbon for use; (3) Production of aminated modified bagasse, wherein pretreated bagasse is added to the activated aqueous monomer solution to carry out the grafting reaction, the nitrogen being brought in and the temperature being increased after the Mohr's salt, hydrogen peroxide and acetic acid are added one after the other as catalysts after the reaction temperature has been reached and agitating to react, whereby a reaction product is obtained, and wherein the reaction product is washed with water, steamed, wherein after removing the homopolymer, the product is washed with deionized water, suction filtered and dried to obtain grafted bagasse; Adding amine monomers in the grafted bagasse to the amination reaction, after which reaction the product is washed with water, suction filtered and dried to obtain the aminated modified bagasse for use; (4) Preparing porous composite carbon: Take the carboxylated porous carbon prepared in the step (2) and add ultrapure water to it to prepare a suspension, to which NHS is added to the suspension, whereby the carboxyl groups on the carboxylated porous carbon are ultrasonically activated and the aminated modified bagasse prepared in the step (3) and EDC are sequentially added while subjecting them to reaction at room temperature, and then suction filtered and dried to obtain porous composite carbon.
    It should be noted that the key to step (4) is to admit NHS first. You can't admit NHS at the same time as EDC. After adding aminated modified bagasse, stir well and then add EDC to start the reaction.
    Preferably, in the above-mentioned production method of porous composite carbon for efficiently adsorbing mercury, the temperature of carbonization in step (1) is 400-700 ° C, preferably 500-650 ° C, more preferably 500 ° C; The base is an alkaline inorganic substance, preferably potassium hydroxide; The calcination temperature is 600-900 ° C, preferably 600-800 ° C, more preferably 600 ° C.
    Preferably, in the above-mentioned production process of Porôser composite carbon for efficiently adsorbing mercury under the reaction conditions in step (2), a temperature of 60 ° C. and a reaction time of 3 hours are provided.
    Preferably, in the above-mentioned porous composite carbon manufacturing method for efficiently adsorbing mercury, the step (3) includes the following pretreatment steps: crushing and sieving bagasse and immersing it in it
    * BE2020 / 5913 lye with a concentration of 2 to 20%; the immersion time is 1-24 hours and it is dried after immersion.
    The advantageous effect of the above technical solution is that the lye and the activated bagasse surface groups can remove most of the hemicellulose and lignin in the bagasse.
    Preferably in the above-mentioned production method of porous composite carbon for efficiently adsorbing mercury, the activating monomer in step (3) is one of acrylamide, acrylonitrile and glycidyl methacrylate, the concentration of the aqueous monomer solution being 6 to 18% and the volume of the aqueous monomer solution being 100 to 1000 ml.
    Preferably, in the above-mentioned production method of porous composite carbon for efficiently adsorbing mercury, the reaction temperature of the graft reaction in step (3) is 40 to 80 ° C and the reaction time is 1 to 6 hours.
    Preferably, in the above-mentioned production method of porous composite carbon for efficiently adsorbing mercury, the amount of Mohr's salt added is 0.02 to 0.1 g, the amount of hydrogen peroxide added is 0.2-1 ml and the volume percentage of acetic acid is 0.2 - 1% based on per 100 ml of active aqueous monomer solution in step (3), and more preferably the amount of Mohr salt added is 0.06 g, the amount of hydrogen peroxide added is 0.5 ml and the percentage by volume of acetic acid is 0.2 - 1% based on per 100 ml of active aqueous monomer solution in step (3).
    Preferably, in the above-mentioned porous composite carbon production method for efficiently adsorbing mercury, the amine monomers in step (3) are one or more of ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine and polyethylene polyamines.
    Preferably, in the above-mentioned production method of porous composite carbon for efficiently adsorbing mercury, the reaction temperature of the amination reaction in step (3) is 110-150 ° C. and the reaction time is 1-5 hours.
    Preferably, in the above-mentioned porous composite carbon manufacturing method for efficiently adsorbing mercury, the mass ratio of the carboxylated modified porous carbon, NHS and EDC in step (4) is 20: 1: 2; wherein the mass ratio of the aminated modified bagasse to the carboxylated modified porous carbon is 1: 2-2: 1.
    The advantageous effect of the above technical solution is that the addition amount of carboxylated modified porous carbon, NHS, EDC and aminated modified bagasse is acquired after a large number of experiments and verifications
    ° BE2020 / 5913. If it exceeds the above range, the adsorption capacity of finally obtained composite carbon materials for mercury ions decreases and the adsorption equilibrium time is prolonged.
    Preferably, in the above-mentioned porous composite carbon manufacturing method for efficiently adsorbing mercury, the ultrasonic time in step (4) is 20 to 40 minutes and the reaction time is 1 to 3 hours. The invention also discloses a porous composite carbon which is produced by the above method and which can adsorb mercury efficiently. From the above technical solutions, it can be known that the present invention discloses a production method of porous composite carbon for efficiently adsorbing mercury, compared with the prior art, which has the following advantages: (1) The present invention utilizes the highly efficient stepped porous structure which is formed by the natural development of the bagasse during the growth process. After carbonation and activation, the naturally graded porous structure and air channels of the bagasse remain. There are many micropores, mesopores and interconnected pores on the surface and inside of the produced porous carbon, which contribute to the mass transfer and diffusion of adsorbate and are conducive to rapid adsorption of mercury ions.
    (2) The present invention uses aminated modified bagasse and porous carbon for bonding. The porous carbon can quickly attract and adsorb mercury ions on the surface of the porous carbon. High amine amine amine modified bagasse has enough effective amine groups to provide high adsorption capacity by physical adsorption and detection of porous carbon and chemical adsorption and covalent bonding of organic amines becomes a synergistic effect of adsorbing and removing mercury efficiently without omission which greatly improves the adsorption and removal effect of porous bagasse composite carbon on mercury.
    (3) In the present invention, the inexpensive bagasse is selected as the raw material, thereby expanding the source for the production of porous high-performance carbon raw materials and enabling effective use of resources.
    BRIEF DESCRIPTION OF THE DRAWINGS In order to explain the embodiments of the present invention or the technical solutions in the prior art more clearly, the following briefly introduces the drawings used in the description of the embodiments or the prior art. Obviously, in the following description, the drawings are the embodiments of the present invention. For the expert: know how in the field
    ° BE2020 / 5913 other drawings can be obtained according to the drawings provided without creative work.
    Figure 1 is the adsorption isotherms of aminated bagasse (AB), porous carbon (PC), and the aminated porous composite bagasse carbon (AB & PC) of Example 1 for mercury; Figure 2 is the adsorption kinetic curve of aminated bagasse (AB), porous carbon (PC) and the aminated porous composite bagasse carbon (AB & PC) of Example 1; and FIG. 3 is a scanning electron microscope picture of aminated bagasse composite porous carbon prepared in Example 1. FIG.
    DETAILED DESCRIPTION The technical solutions in the embodiments of the present invention will be described in detail and fully below. Obviously, the described embodiments are only a part of the embodiments of the present invention and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments that can be obtained by one of ordinary skill in the art without creative work fall within the scope of the present invention.
    Example 1 Put 1 g of bagasse in a carbonation oven, carbonize for 3 hours at 500 ° C, add 4 g of KOH as an activator and mix and then calcine at 600 ° C, wash and dry. The obtained porous carbon is mixed with 12% concentrated nitric acid and reacted for 3 hours at 60 ° C to obtain carboxylated porous carbon.
    Soak the bagasse crushed to a particle size of 20 mesh in a NaOH solution with a concentration of 5%, immerse for 24 hours, and then filter and dry. Add 10 g of pretreated bagasse in 10 ml of aqueous acrylamide solution and fill up to 100 ml with deionized water. Introduce nitrogen gas and raise the temperature. After the reaction temperature has been reached, 0.05 g of black salt, 0.6 ml of hydrogen peroxide and 0.4 ml of acetic acid are added one after the other, and the reaction is carried out at 50 ° C. for 5 h. After washing and boiling with water, the homopolymers in the reaction product are removed, then it is washed with deionized water, filtered off with suction and dried, diethylenetriamine is added to 10 g of bagasse grafted above, reacted for 5 h at 120 ° C, washed with water, suction filtered and dried to obtain aminated modified bagasse.
    Preparation of aminated modified porous bagasse composite carbon: In 1 g of carboxylated modified porous carbon, ultrapure water is added to make a suspension. Add 50 mg of NHS, ultrasound for 30 minutes to the
    / BE2020 / 5913 to activate carboxyl groups on the porous carbon. 2 g of aminated modified bagasse is added to the above suspension, 100 mg of EDC is added, and the reaction is carried out for 2 hours at room temperature, washing with water, suction filtering and drying to obtain aminated modified porous bagasse composite carbon.
    In the 0.1 g of aminated modified porous bagasse composite carbon produced in this example, a series of mercury ion solutions at different initial concentrations is added, placed in a shaker and shaken for 12 hours. The remaining mercury ion concentration is measured with an intelligent mercury meter. According to the adsorption isotherm, the adsorption capacity of the porous composite carbon material for mercury ions can be calculated, which is 1178.5 mg / g. According to the adsorption kinetic curve, it can be known that the time to reach adsorption equilibrium is 10 minutes.
    Example 2 Put 1 g bagasse in a carbonation oven, carbonize for 1 hour at 700 ° C, add 4 g KOH as activator and mix and calcine at 700 ° C, wash and dry. The obtained porous carbon is mixed with 12% concentrated nitric acid and reacted for 5 hours at 40 ° C to obtain carboxylated porous carbon.
    Soak the bagasse crushed to a particle size of 20 mesh in a NaOH solution with a concentration of 5%, immerse for 1 hour and then filter and dry. Add 10 g of pretreated bagasse in 6 ml of aqueous acrylonitrile solution and fill up to 100 ml with deionized water. Introduce nitrogen gas and raise the temperature. After the reaction temperature has been reached, 0.02 g of black salt, 1.0 ml of hydrogen peroxide and 1.0 ml of acetic acid are added in succession, and the reaction is carried out at 80 ° C. for 1 hour. After washing and boiling with water, the homopolymers in the reaction product are removed, then it is washed with deionized water, suction filtered and dried, in 10 g of bagasse grafted above, tetraethylene pentamine is added, react for 2 h at 140 ° C, wash with water, suction filter and dry to get aminated modified bagasse.
    Preparation of aminated modified porous bagasse composite carbon: In 2 g of carboxylated modified porous carbon, ultrapure water is added to make a suspension. Add 100 mg of NHS, ultrasound for 20 minutes to activate the carboxyl groups on the porous carbon. 1 g of aminated modified bagasse is added to the above suspension, 200 mg of EDC is added and the reaction is carried out for 1 hour at room temperature, washed with water, suction filtered and dried to obtain aminated modified porous composite carbon of bagasse.
    In the 0.1 g of aminated modified porous bagasse composite carbon produced in this example, a series of mercury ion solutions at different initial concentrations is added, placed in a shaker and for 12 hours
    Shake ° BE2020 / 5913. The remaining mercury ion concentration is measured with an intelligent mercury meter. According to the adsorption isotherm, the adsorption capacity of the porous composite carbon material for mercury ions can be calculated, which is 926.8 mg / g. According to the adsorption kinetic curve, it can be known that the time to reach adsorption equilibrium is 12 minutes. Example 3 Put 1 g bagasse in a carbonation oven, carbonize for 2 hours at 600 ° C, add 4 g KOH as activator and mix and calcine at 700 ° C, wash and dry.
    The obtained porous carbon is mixed with 12% concentrated nitric acid and reacted for 2 hours at 70 ° C. to obtain carboxylated porous carbon.
    Soak the bagasse crushed to a particle size of 20 mesh in a NaOH solution with a concentration of 8%, immerse for 1 hour, and then filter and dry. Add 10 g of pretreated bagasse in 18 ml of aqueous glycidyl methacrylate solution and fill up to 100 ml with deionized water. Introduce nitrogen gas and raise the temperature. After the reaction temperature has been reached, 1.0 g of black salt, 1.0 ml of hydrogen peroxide and 0.2 ml of acetic acid are added one after the other, and the reaction is carried out at 40 ° C. for 5 h. After washing and boiling with water, the homopolymers in the reaction product are removed, then it is washed with deionized water, suction filtered and dried, diethylenetriamine is added to 10 g of bagasse grafted above, react for 1 hour at 150 ° C, wash with water, suction filters and drying to obtain aminated modified bagasse.
    Preparation of aminated modified porous bagasse composite carbon: In 1 g of carboxylated modified porous carbon, ultrapure water is added to make a suspension. Add 50 mg of NHS, ultrasound for 40 minutes to activate the carboxyl groups on the porous carbon. 1 g of aminated modified bagasse is added to the above suspension, 100 mg of EDC is added, and the reaction is carried out for 3 hours at room temperature, washing with water, suction filtering and drying to obtain aminated modified porous bagasse composite carbon.
    In the 0.1 g of aminated modified porous bagasse composite carbon produced in this example, a series of mercury ion solutions at different initial concentrations is added, placed in a shaker and shaken for 12 hours. The remaining mercury ion concentration is measured with an intelligent mercury meter. According to the adsorption isotherm, the adsorption capacity of the porous composite carbon material for mercury ions can be calculated, which is 1045.5 mg / g. According to the kinetic adsorption curve, it can be known that the time to reach adsorption equilibrium is 8 minutes.
    ) BE2020 / 5913 Comparative Example 1 (porous carbon) Put 1 g of bagasse in a carbonation oven, carbonize for 3 hours at 500 ° C, add 4 g of KOH as activator and mix and calcine at 600 ° C, wash and dry. The obtained porous carbon is mixed with 12% concentrated nitric acid and reacted for 3 hours at 60 ° C to obtain carboxylated porous carbon.
    In the 0.1 g porous carbon produced in this comparative example, a series of mercury ion solutions at different initial concentrations is added, placed in a shaker and shaken for 12 hours. The remaining mercury ion concentration is measured with an intelligent mercury meter. According to the adsorption isotherm, the adsorption capacity of the porous composite carbon material for mercury ions can be calculated, which is 441.9 mg / g. According to the adsorption kinetic curve, it can be known that the time to reach adsorption equilibrium is 5 minutes.
    Comparative Example 2 (Aminated Bagasse) Place the bagasse crushed to a particle size of 20 mesh in a NaOH solution with a concentration of 5%, immerse for 24 hours and then filter and dry. Add 10 g of pretreated bagasse in 10 ml of aqueous acrylamide solution and fill up to 100 ml with deionized water. Introduce nitrogen gas and raise the temperature.
    After the reaction temperature has been reached, 0.05 g of black salt, 0.6 ml of hydrogen peroxide and 0.4 ml of acetic acid are added one after the other, and the reaction is carried out at 50 ° C. for 5 h. After washing and boiling with water, the homopolymers in the reaction product are removed, then it is washed with deionized water, suction filtered and dried, diethylenetriamine is added to 10 g of bagasse grafted above, react for 5h at 120 ° C, wash with water, suction filters and dry to get aminated modified bagasse.
    In the 0.1 g of aminated modified bagasse produced in this comparative example, a number of mercury ion solutions at different initial concentrations are added, placed in a shaker and shaken for 12 hours. The remaining mercury ion concentration is measured with an intelligent mercury meter. According to the adsorption isotherm, the adsorption capacity of the porous composite carbon material for mercury ions can be calculated, which is 864.9 mg / g. According to the adsorption kinetic curve, it can be known that the time to reach adsorption equilibrium is 30 minutes.
    Comparative Example 3 (two-stage amine-modified porous carbon) (1) Production of graduated porous carbon based on bagasse: carbonize bagasse at 700 ° C, add KOH as an activator (the consumption amount of KOH is four times the weight of bagasse) and at 600 ° C calcine. The obtained particles are washed with HNO: of 10 mass% and distilled water, then the graduated porous carbon is obtained. (2) Surface oxidation activation of graded porous carbon based on bagasse: Dissolve 10 g of graded porous carbon in 100 ml of acetic acid solution having a concentration of 30% by mass, then add 2 ml of composite oxidizing agent and react for 3 hours at 50 ° C. In which the composition of the composite oxidizing agent is as follows: ammonium persulfate with a concentration of 20% by mass, a sulfuric acid solution with a concentration of 10% by mass and the solvent is water, then wash with water, suction filter and dry to oxygenate, graduated obtain porous carbon.
    (3) Preparation of hyperbranched polyamide-amine: 100 ml of triethylenetetramine are dissolved in 100 ml of methanol, poured into a three-necked flask, placed in an ice bath and a mixed solution of 59 ml of methyl acrylate and 100 ml of methanol is slowly added. After the addition, the methanol is removed by rotary evaporation at 50 ° C. and then reacted for 24 hours at 100 ° C. in order to obtain hyperbranched polyamide-amine.
    (4) Production of a two-stage amine-modified stepped porous carbon from bagasse: 10 g of oxygen-containing porous carbon, which is produced in step (2), in a polytetrafluoroethylene reactor containing 100 ml of hyperbranched polyamide-amine, react airtight at 130 ° C for 2 hours , wash alternately with cold and hot water (cold water is tap water, hot water is water over 80 ° C), vacuum filter and dry; Add 10 g of dried sample to a polytetrafluoroethylene reactor, which reactor contains 100 ml of triethylenetetramine, react at 140 ° C for 1 hour, after reacting the reaction product is washed with water, boiled in boiling water for 10 minutes, washed with deionized water , suction filtered and dried.
    In the 0.1 g two-stage amine-modified porous carbon produced in this comparative example, a series of mercury ion solutions at different initial concentrations is added, placed in a shaker and shaken for 12 hours. The remaining mercury ion concentration is measured with an intelligent mercury meter. According to the adsorption isotherm, the adsorption capacity of the porous composite carbon material for mercury ions can be calculated, which is 782.1 mg / g. According to the adsorption kinetic curve, it can be known that the time to reach adsorption equilibrium is 12 minutes.
    The various examples in this specification are described progressively. Each example focuses on the differences from other examples, and the same or similar parts between the different examples may be related. For the solution disclosed in the examples, the description is relatively simple, since it corresponds to that in the
    "BE2020 / 5913 embodiment corresponds to the method disclosed, and the relevant part may refer to the description of the method part.
    The preceding description of the disclosed examples will enable any person skilled in the art to implement or use the present invention.
    Various modifications to such examples will be apparent to those skilled in the art, and the general principles defined in this context can be implemented in other examples without departing from the spirit or scope of the present invention.
    Therefore, the present invention will not be limited to the examples shown in this specification, but should be accorded the broadest scope that conforms to the principles and novel features disclosed in this specification.
    权利要求:
    Claims (10)
    [1]
    A method of manufacturing porous composite carbon for efficiently adsorbing mercury, characterized thereby, comprising the steps of: (1) manufacturing bagasse-based porous carbon, wherein the bagasse is carbonized and the carbonized bagasse is obtained, then using alkali as an activator is used, wherein the alkali is mixed with carbonized bagasse, calcined and activated, then washed with water and dried to obtain the porous carbon; (2) Making carboxylated porous carbon by reacting the porous carbon with concentrated nitric acid in a mass concentration of 10-12% at a temperature of 40-70 ° C for 1-5 hours, washing it with water and drying it, and then the carboxylated porous carbon is obtained for further use; (3) Manufacture of aminated modified bagasse, wherein pretreated bagasse is added to the activated aqueous monomer solution to carry out a graft reaction, the nitrogen is brought in and the temperature is increased, after reaching the reaction temperature, the Mohr's salt, hydrogen peroxide and acetic acid as Catalysts are sequentially added and stirred to react to obtain a reaction product, and wherein the reaction product is washed with water, steamed, wherein after removing the homopolymer, the product is washed with deionized water, suction filtered and dried to obtain grafted bagasse; Adding amine monomers in the grafted bagasse to the amination reaction, after which reaction the product is washed with water, suction filtered and dried to obtain the aminated modified bagasse for further use; (4) Preparing porous composite carbon: Take the carboxylated porous carbon prepared in the step (2) and add ultrapure water to it to prepare a suspension, to which NHS is added to the suspension, whereby the carboxyl groups on the carboxylated porous carbon are ultrasonically activated and the aminated modified bagasse prepared in the step (3) and EDC are sequentially added while subjecting them to reaction at room temperature, and then suction-filtered and dried to obtain porous composite carbon.
    [2]
    2. A method for producing porous composite carbon for efficiently adsorbing mercury according to claim 1, characterized in that the pretreatment step in step
    (3) is: crushing and sieving bagasse and immersing it in lye at a concentration of 2 to 20%; the immersion time is 1-24 hours and it is dried after immersion.
    [3]
    3. The method for producing porous composite carbon for efficiently adsorbing mercury according to claim 1, characterized in that the activating monomer in step (3) is one of acrylamide, acrylonitrile and glycidyl methacrylate, the concentration of the aqueous monomer solution being 6 to 18%.
    [4]
    4. Process for the production of porous composite carbon for the efficient adsorption of mercury according to claim 1, characterized in that the reaction temperature of the graft reaction in step (3) is 40-80 ° C and the reaction time is 1-6 hours.
    [5]
    5. A method for the production of porous composite carbon for efficiently adsorbing mercury according to claim 1, characterized in that the amount of added Mohr salt 0.02 to 0.1 g and the amount of added hydrogen peroxide 0.2-1 ml and the Percentage by volume of acetic acid is 0.2-1% based on per 100 ml of active aqueous monomer solution in step (3).
    [6]
    6. A method for producing porous composite carbon for efficiently adsorbing mercury according to claim 1, characterized in that the amine monomer in step (3) is one or more of ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine and polyethylene polyamines.
    [7]
    7. The method for producing porous composite carbon for efficiently adsorbing mercury according to claim 1, characterized in that the reaction temperature of the amination reaction in step (3) is 110-150 ° C and the reaction time is 1-5 hours.
    [8]
    8. The method for producing porous composite 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 step (4) is 20: 1: 2, and wherein the mass ratio the aminated modified bagasse to the carboxylated modified porous carbon is 1: 2-2: 1.
    [9]
    9. A method for producing porous composite carbon for efficiently adsorbing mercury according to claim 1, characterized in that the ultrasonic time in step (4) is 20 to 40 minutes and the reaction time at room temperature is 1 to 3 hours.
    [10]
    10. Porous composite carbon for efficiently adsorbing mercury, which is produced according to the method according to any one of claims 1 to 9.
    类似技术:
    公开号 | 公开日 | 专利标题
    CN105498707B|2019-03-05|A kind of preparation method and application of modified graphene oxide/Chitosan Composites
    CN103769058B|2015-12-09|The preparation method of carbonization chitosan absorbent, product and application process
    CN106799215A|2017-06-06|A kind of porous spherical crosslinked resin graphene oxide composite adsorption material and its preparation and application
    CN1583550A|2005-02-23|Preparing method for porous carbon with high specific surface area
    CN106964321B|2018-05-11|A kind of preparation method and applications of banana fiber chitosan composite hydrogel
    CN101982580A|2011-03-02|Polyacrylonitrile/hydroxyapatite composite adsorbent fiber and preparation method thereof
    CN107262061A|2017-10-20|A kind of heavy metal ion adsorbing material based on graphene and preparation method thereof
    CN102908998B|2014-07-30|Preparation method of xanthate macro-pore dextrangel adsorbent
    CN105771895A|2016-07-20|Graphene three-dimensional composite material and preparation method and application thereof
    CN107774232A|2018-03-09|A kind of magnetic active carbon mixture of the ball containing charcoal and preparation method thereof
    BE1027994B1|2021-08-10|Porous composite carbon for efficiently adsorbing mercury and manufacturing process thereof
    CN104594037B|2017-12-29|A kind of preparation method of graft polypropylene nonwoven fabric base ion exchange material
    KR100533873B1|2005-12-06|Producing method of biosorbent for heavy metal removal and biosorbent produced therefrom
    CN104383900A|2015-03-04|Preparation method of polypyrrole-modified corncob composite adsorbent
    CN109160553A|2019-01-08|A kind of dedicated sewage-treating agent of chemical fibre industry and preparation method thereof
    CN102872817A|2013-01-16|Composite absorbing material for removing iron ions from natural water body and preparation method thereof
    DE60035792T2|2008-04-30|USE OF A MATERIAL WITH SEPARATION FUNCTION
    CN111018037B|2021-04-27|Method for removing heavy metal mercury ions in water based on polyacrylonitrile nano-film compound
    CN111905695A|2020-11-10|Cellulose-based hollow porous carbon fiber microsphere adsorbent and preparation method thereof
    Zhu et al.2017|Microfluidic synthesis of renewable biosorbent with highly comprehensive adsorption performance for copper |
    CN109482161B|2021-08-03|Two-section amine modified bagasse hierarchical porous carbon capable of efficiently adsorbing mercury, and preparation method and application thereof
    CN105642245B|2017-11-24|A kind of preparation method of magnetic egg white/luffa sorbing material
    Aquino et al.2018|Preparation of cellulose acetate blended with chitosan nanostructured membrane via electrospinning for Cd2+ adsorption in artificial wastewater
    KR20170133613A|2017-12-06|Metal adsorbent and preparing method thereof
    CN110624514A|2019-12-31|Method for improving adsorption capacity of humic acid on metal ions
    同族专利:
    公开号 | 公开日
    CN112588267A|2021-04-02|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CN104107685B|2014-06-26|2016-03-23|广州甘蔗糖业研究所|A kind of high percent grafting bagasse base adsorbent and preparation method thereof and application|
    CN109482161A|2019-01-15|2019-03-19|广东省生物工程研究所（广州甘蔗糖业研究所）|The modified bagasse graded porous carbon of two sections of amine of energy efficient absorption mercury and preparation method and application|
    法律状态:
    2021-09-30| FG| Patent granted|Effective date: 20210810 |
    优先权:
    申请号 | 申请日 | 专利标题
    CN202011345250.0A|CN112588267A|2020-11-25|2020-11-25|Composite porous carbon capable of efficiently adsorbing mercury and preparation method thereof|
    [返回顶部]