CN113149005A - Biomass porous carbon material with high specific surface area, and preparation method and application thereof - Google Patents
Biomass porous carbon material with high specific surface area, and preparation method and application thereof Download PDFInfo
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Abstract
本发明公开了一种高比表面积生物质多孔碳材料的制备方法，该方法在惰性气氛保护的加热条件下，以木质素磺酸钠为碳前驱体，以无水碳酸钾为活化剂，与N掺杂剂制备得到生物质多孔碳材料；本发明还公开了一种高比表面积生物质多孔碳材料及其在去除水体中氯霉素的应用。本发明以廉价易得、来源稳定的木质素磺酸钠为原料，利用活化剂与碳反应以促进孔隙的形成，且N掺杂剂参与制孔过程，促进了碳材料中孔隙的增大和孔结构的增加，提升了生物质多孔碳材料的比表面积和孔隙结构，有利于提高对污染物的吸附量；本发明的制备方法简单，且效率高，原料成本降低，易于推广；本发明的生物质多孔碳材料对水体中的氯霉素具有优异的吸附作用，且吸附性能稳定。
The invention discloses a preparation method of a biomass porous carbon material with high specific surface area. Under the heating condition protected by an inert atmosphere, the method uses sodium lignosulfonate as a carbon precursor, anhydrous potassium carbonate as an activator, and The biomass porous carbon material is prepared by N dopant; the invention also discloses a high specific surface area biomass porous carbon material and its application in removing chloramphenicol in water body. The invention uses sodium lignosulfonate, which is cheap and easy to obtain and stable in source, as a raw material, uses an activator to react with carbon to promote the formation of pores, and the N dopant participates in the pore-making process, thereby promoting the increase of pores and pores in the carbon material. The increase of the structure improves the specific surface area and pore structure of the biomass porous carbon material, which is beneficial to increase the adsorption amount of pollutants; the preparation method of the present invention is simple, has high efficiency, reduces the cost of raw materials, and is easy to popularize; The material porous carbon material has excellent adsorption effect on chloramphenicol in water, and the adsorption performance is stable.
Description
Technical Field
The invention belongs to the technical field of preparation of environment functional materials, and particularly relates to a biomass porous carbon material with a high specific surface area, and a preparation method and application thereof.
Background
Chloramphenicol is an antibiotic which has an inhibitory effect on gram-positive bacteria, gram-negative bacteria, anaerobic bacteroides, rickettsiae, chlamydia and mycoplasmas, and is widely used in the livestock industry, aquaculture industry, medicines, cosmetics and other aspects due to the advantages of low price, wide antibacterial spectrum, easy preservation and the like after being successfully separated in 1947. However, chloramphenicol can cause diseases such as aplastic anemia, skin rash, drug fever, angioneurotic edema, exfoliative dermatitis, etc. At present, more and more reports of chloramphenicol detection in water body environments around the world are provided, and the problem of how to effectively control the content of chloramphenicol is more urgent. The adsorption method is a high-efficiency, rapid and stable chloramphenicol removal method, but the application of the adsorbent is limited by the high price of commercial activated carbon.
The porous carbon material is widely used in the fields of supercapacitors, catalysts, hydrogen storage, catalysis and the like due to the high specific surface area, abundant porosity and high corrosion resistance. However, in the current research, a large amount of carbon materials are not made of environment-friendly, sustainable or cheap and easily available raw materials, such as fossil energy, high molecular polymers, and the like, and are not suitable for large-scale practical application. Therefore, biomass materials are attracting much attention due to their advantages of environmental friendliness, abundance and ready availability. Lignin is a renewable carbon source, the second largest biopolymer on earth next to cellulose. Despite the potential for large-scale utilization of lignin, only 3% of lignin is utilized today. Sodium Lignosulfonate (SLS), a by-product of the use of lignin in the pulping industry, produces approximately 7000 million tons per year. Compared with lignin, SLS also contains many oxygen-containing functional groups, such as beta-O-4 'and alpha-O-4' bonds, so that the water solubility of the SLS is greatly improved, and the application range is expanded. Therefore, the recycling of the sodium lignosulfonate has wide prospect.
The pore geometry (including diameter, length and tortuosity) is a key factor in evaluating the performance of porous carbon materials. The carbon precursor may be converted into a carbon material by a physical activation or chemical activation method. The chemically activated carbon has a higher specific surface area and porosity than the former. Commonly used activators include bases (KOH, K)2CO3And KHCO3) Acid (H)3PO4) And metal salts (ZnCl)2). Using ZnCl2As an activator, the energy consumption is low, but the volatility and the toxicity of the activator pose a threat to the environment. H3PO4Has the advantage of low running cost, but the specific surface area of the carbon prepared by the activation is lower than that of the alkali treatment.
At present, the research reports on removing chloramphenicol from water by using biomass porous carbon are increasing day by day. Fang et al, "Effect of biochemical-derived organic matter on adaptation of biochemical and biochemical", published in Journal of Hazardous Materials 2020; ahmed et al 2017, "Chloramphenic interaction with functionalized biochar in water: reactive mechanism, molecular imprinting effect and repeatable application", Science of The Total Environment; yang et al published in 2017 "High-yield and High-performance pore biochar product from pyrolosis of peanic shell with low-dose ammonium polyphosphate for chloremphonic adsorption" on Journal of Cleaner Production. The three articles are all researches on removing chloramphenicol from a porous carbon material prepared by using biomass as a carbon source, but a porous carbon material which has high adsorption capacity and regeneration performance on chloramphenicol and is prepared by using a one-step method by using a large amount of available sodium lignosulfonate as a carbon source and introducing an N dopant is not reported.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a biomass porous carbon material with a high specific surface area aiming at the defects of the prior art. According to the method, sodium lignosulfonate is used as a carbon precursor, an alkali activator and an N dopant are used for preparing the biomass porous carbon material, the activator reacts with carbon to promote pore formation, the N dopant participates in a pore making process, so that the pore enlargement and the pore structure increase in the carbon material are promoted, the specific surface area and the pore structure of the biomass porous carbon material are improved, and the adsorption capacity to pollutants is improved.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: the preparation method of the biomass porous carbon material with the high specific surface area is characterized in that under the heating condition of inert atmosphere protection, sodium lignosulfonate is used as a carbon precursor, anhydrous potassium carbonate is used as an activating agent, and the activating agent and an N doping agent are used for preparing the biomass porous carbon material.
According to the invention, sodium lignosulfonate is used as a carbon precursor to prepare the biomass porous carbon material, N dopant is added on the basis of using an alkali activator and is pyrolyzed, the activator reacts with carbon to promote pore formation, meanwhile, the N dopant participates in a pore-making process and forms a complex with the activator anhydrous potassium carbonate to generate KCNO at 500 ℃, when the temperature is raised to 700 ℃, the carbon substrate reduces KCNO (KCNO + C → KCN + CO) to generate carbon thermal cycle, so that a new alkali substance (KCN) is generated and CO gas is released, the increase of pores and the increase of pore structure in the carbon material are further promoted, the specific surface area and the pore structure of the biomass porous carbon material are improved, and the adsorption quantity of pollutants is favorably improved; meanwhile, the method takes the pulping by-product sodium lignosulfonate which is cheap and easy to obtain and has stable source as a raw material, realizes waste recycling and saves resources.
The preparation method of the biomass porous carbon material with the high specific surface area is characterized by comprising the following steps:
step one, placing the dried sodium lignosulfonate, anhydrous potassium carbonate and N dopant in an agate mortar, and uniformly mixing and grinding to obtain mixed powder;
step two, putting the mixed powder obtained in the step one into a corundum porcelain boat, putting the corundum porcelain boat into a tube furnace protected by inert atmosphere, heating and preserving heat, and naturally cooling to room temperature to obtain a carbonized product;
and step three, repeatedly washing the carbonized product obtained in the step two by using a dilute hydrochloric acid solution and deionized water until the carbonized product is neutral, and drying to obtain the biomass porous carbon material.
According to the invention, the dried sodium lignosulfonate, the anhydrous potassium carbonate and the N dopant are mixed and ground uniformly, the raw materials are promoted to be fully and uniformly mixed while the sizes of the raw materials are refined, then heating, heat preservation and pyrolysis are carried out in an inert atmosphere, and the obtained carbonized product is washed and dried to obtain the biomass porous carbon material. By directly heating the carbon precursor, the alkali activator and the N dopant to a high temperature condition in one step, the phenomenon that the carbon precursor stays at a low temperature in a conventional method and is pyrolyzed to generate substances such as tar and the like to block pores in a large quantity is avoided, meanwhile, the alkali activator and the N dopant effectively remove the tar and form a microporous structure in the pyrolysis process, the number of the pores is increased, and the generation efficiency of the pore structure is improved.
The preparation method of the biomass porous carbon material with the high specific surface area is characterized in that in the step one, the N dopant is one or more than two of melamine, urea and dicyanodiamine. The nitrogen content of the preferred N dopant is high, which is beneficial to forming a complex with an activator anhydrous potassium carbonate, improving the release amount of CO gas, and promoting the increase of pores and the increase of a pore structure in the carbon material.
The preparation method of the biomass porous carbon material with the high specific surface area is characterized in that the mass ratio of the sodium lignosulfonate, the anhydrous potassium carbonate and the N dopant after drying in the step one is 1:4:0.4 to 0.6. The optimized raw material mass ratio ensures the full action of anhydrous potassium carbonate, the N dopant and sodium lignosulfonate, avoids the waste of raw materials, improves the hole making effect, greatly improves the specific surface area of the biomass porous carbon material, and further improves the adsorption capacity of the biomass porous carbon material.
The preparation method of the biomass porous carbon material with the high specific surface area is characterized in that in the second step, the inert atmosphere is nitrogen or/and argon, and the specific heating and heat preservation process comprises the following steps: heating from room temperature to 750-850 ℃ at the speed of 5 ℃/min and preserving heat for 1-3 h. The optimized heating and heat preservation temperature promotes the decomposition of the activating agent and the N doping agent, particularly the activating agent and the N doping agent are completely decomposed at the temperature of more than 800 ℃, the hole making process is promoted, the optimized heating rate and heat preservation time guarantee that carbon in the pyrolysis process is subjected to uniform reaction, and the uniformity of hole distribution in the biomass porous carbon is improved.
The preparation method of the biomass porous carbon material with the high specific surface area is characterized in that the drying temperature in the third step is 80-120 ℃, and the drying time is 10-14 h. The optimal drying temperature and time ensure complete volatilization of moisture in the biomass porous carbon material, and the stability of the biomass porous carbon material is improved.
In addition, the invention also discloses a biomass porous carbon material with high specific surface area prepared by the method.
The carbon precursor raw material sodium lignosulfonate of the biomass porous carbon material has wide source, high yield, low price, easy obtaining and sustainable obtaining, and is suitable for large-scale application.
The invention also discloses application of the high-specific surface area biomass porous carbon treatment material in removal of chloramphenicol in a water body.
The biomass porous carbon material has high specific surface area, has excellent adsorption effect on chloramphenicol in a water body, and has good stability due to the fact that the adsorption effect is mainly hole filling; meanwhile, a short and flat ordered graphitized structure exists in the biomass porous carbon material and serves as a pi-electron acceptor, pi-pi EDA interaction and hydrogen bond interaction are formed between the graphitized structure and chloramphenicol, and certain pyridine-N and pyrrole-N exist in the biomass porous carbon material and serve as a base and a hydrogen acceptor, so that adsorption of chloramphenicol is facilitated; in addition, hydrophobic interaction and electrostatic interaction exist between the biomass porous carbon material and chloramphenicol. Under the comprehensive action, the biomass porous carbon material has excellent adsorption performance on chloramphenicol, and the adsorption performance is stable.
Compared with the prior art, the invention has the following advantages:
1. according to the method, the biomass porous carbon is prepared by taking sodium lignosulfonate as a carbon precursor, the N dopant is added on the basis of using an alkali activator, the activator reacts with carbon to promote pore formation, and meanwhile, the N dopant participates in the pore preparation process, so that the pore enlargement and the pore structure increase in the carbon material are promoted, the specific surface area and the pore structure of the biomass porous carbon material are improved, and the adsorption capacity on pollutants is favorably improved.
2. The method takes the pulping by-product sodium lignosulfonate which is cheap and easy to obtain and stable in source as the raw material, has the advantages of wide source, high yield, low price, easy obtaining, sustainability, suitability for large-scale application, realization of waste recycling and resource saving.
3. The preparation method has the advantages of simple process, short flow, low production cost and time, high preparation efficiency, low requirement on equipment and easy realization.
4. The specific surface area of the biomass porous carbon material is up to 2568m2·g-1The surface area of the micropores is up to 1700m2·g-1Total pore volume up to 1.5cm3·g-1The average pore diameter reaches 2.33 nm.
5. The biomass porous carbon material has high specific surface area, excellent adsorption effect on chloramphenicol in a water body and stable adsorption performance; meanwhile, the biomass porous carbon material also has good humic acid interference resistance and regeneration capacity.
6. The biomass porous carbon material with the high specific surface area has an obvious flaky nano structure, the transmission distance of chloramphenicol molecules among pores is shortened, the contact between the biomass porous carbon material and the chloramphenicol molecules is promoted, and the adsorption efficiency on chloramphenicol is effectively improved; meanwhile, nitrogen elements introduced into the biomass porous carbon material mainly exist in the forms of pyridine-N and pyrrole-N, and the pyridine-N and the pyrrole-N are used as bases and hydrogen acceptors to be beneficial to enhancing the adsorption performance on chloramphenicol.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
FIG. 1 is a scanning electron micrograph of PC-800-0.5 prepared in example 3 of the present invention.
FIG. 2 is a graph showing the nitrogen adsorption and desorption curves of PC-800-0.5 prepared in example 3 of the present invention.
FIG. 3 is an XRD pattern of PC-800-0.5 prepared in example 3 of the present invention.
FIG. 4 is a graph showing the adsorption kinetics fit of PC-800-0.5 to chloramphenicol, prepared in example 3 of the present invention.
FIG. 5 is a drawing showing chloramphenicol absorption of PC-800-0.5 prepared in example 3 of the present invention at various pH.
FIG. 6 is a drawing showing chloramphenicol absorption of PC-800-0.5 prepared in example 3 of the present invention under humic acid interference.
FIG. 7 is the drawing showing that PC-800-0.5 prepared in example 3 absorbs chloramphenicol under the interference of metal ions.
FIG. 8 is a graph of the desorption regeneration performance of PC-800-0.5 prepared in example 3 of the present invention.
Detailed Description
The biomass porous carbon material prepared in the embodiments 1 to 3 is abbreviated as PC-T-x, wherein T is a heating temperature value adopted in the preparation, and x is a mass ratio of an N dopant to sodium lignosulfonate.
The biomass porous carbon and the method for producing the same according to the present invention are described in detail in examples 1 to 3.
Example 1
In this embodiment, under a heating condition protected by an inert atmosphere, sodium lignosulfonate is used as a carbon precursor, anhydrous potassium carbonate is used as an activator, and the sodium lignosulfonate and N-dopant urea are used to prepare a lignin-based porous carbon material, which includes the following steps:
step one, placing the dried sodium lignosulfonate, anhydrous potassium carbonate and N dopant urea in an agate mortar according to a mass ratio of 1:4:0.4, and uniformly mixing and grinding to obtain mixed powder;
step two, putting the mixed powder obtained in the step one into a corundum porcelain boat, putting the corundum porcelain boat into a tube furnace protected by argon, heating the mixed powder from room temperature to 750 ℃ at the speed of 5 ℃/min, preserving heat for 1h, and naturally cooling the mixed powder to room temperature to obtain a carbonized product;
and step three, repeatedly washing the carbonized product obtained in the step two by using 0.2mol/L dilute hydrochloric acid solution and deionized water until the carbonized product is neutral, and drying the carbonized product in an oven at the temperature of 80 ℃ for 10 hours to obtain the biomass porous carbon material.
The N dopant in this embodiment may also be two or more of melamine, urea, and dicyanodiamine.
Example 2
In this embodiment, under a heating condition protected by an inert atmosphere, sodium lignosulfonate is used as a carbon precursor, anhydrous potassium carbonate is used as an activator, and the sodium lignosulfonate and N-dopant dicyanodiamine are used to prepare a lignin-based porous carbon material, which includes the following steps:
step one, placing the dried sodium lignosulfonate, anhydrous potassium carbonate and N-dopant dicyanodiamide in an agate mortar according to a mass ratio of 1:4:0.6, and uniformly mixing and grinding to obtain mixed powder;
step two, putting the mixed powder obtained in the step one into a corundum porcelain boat, putting the corundum porcelain boat into a tubular furnace protected by nitrogen, heating the mixed powder from room temperature to 850 ℃ at the speed of 5 ℃/min, preserving heat for 3 hours, and naturally cooling the mixed powder to room temperature to obtain a carbonized product;
and step three, repeatedly washing the carbonized product obtained in the step two by using 0.2mol/L dilute hydrochloric acid solution and deionized water until the carbonized product is neutral, and drying the carbonized product in an oven at 120 ℃ for 14 hours to obtain the biomass porous carbon material.
The N dopant in this embodiment may also be two or more of melamine, urea, and dicyanodiamine.
Example 3
In this embodiment, under a heating condition protected by an inert atmosphere, sodium lignosulfonate is used as a carbon precursor, anhydrous potassium carbonate is used as an activator, and the sodium lignosulfonate and N-dopant melamine are used to prepare a lignin-based porous carbon material, which includes the following steps:
step one, placing the dried sodium lignosulfonate, anhydrous potassium carbonate and N dopant melamine in an agate mortar according to a mass ratio of 1:4:0.5, and uniformly mixing and grinding to obtain mixed powder;
step two, putting the mixed powder obtained in the step one into a corundum porcelain boat, putting the corundum porcelain boat into a tube furnace protected by nitrogen and argon, heating the mixed powder from room temperature to 800 ℃ at the speed of 5 ℃/min, preserving heat for 2 hours, and naturally cooling the mixed powder to room temperature to obtain a carbonized product;
and step three, repeatedly washing the carbonized product obtained in the step two by using 0.2mol/L dilute hydrochloric acid solution and deionized water until the carbonized product is neutral, and drying the carbonized product in an oven at 100 ℃ for 12 hours to obtain the biomass porous carbon material.
The N dopant in this embodiment may also be two or more of melamine, urea, and dicyanodiamine.
FIG. 1 is a scanning electron microscope image of PC-800-0.5 prepared in this example, and it can be seen from FIG. 1 that the biomass porous carbon has a lamellar structure.
FIG. 2 is a graph of nitrogen adsorption and desorption curves of PC-800-0.5 prepared in this example, and it can be seen from FIG. 2 that the PC-800-0.5 isotherm shows a combination curve of type I and type IV according to IUPAC chemical association classification, indicating that it has two structures of micropores and mesopores; at a lower relative pressure (P/P)0) The larger amount of adsorbed nitrogen gas indicates that a large amount of microporous structures exist in PC-800-0.5, depending on the relative pressure (P/P)0) When P/P is increased0As can be seen from fig. 1, the pores in PC-800-0.5 prepared in this example are mainly micropores with a pore size of less than 2.0nm, and the mesopores with a pore size of 2.0nm to 4.0nm are smaller.
Fig. 3 is an XRD pattern of PC-800-0.5 prepared in this example, and from fig. 3 it can be seen that the (002) peak of the hexagonal graphitic carbon appears at 2 θ of 29.8 °, indicating that PC-800-0.5 has a higher degree of graphitization, while the peak at 43.3 ° corresponds to the (100) plane of the single-layer graphene honeycomb lattice, indicating the presence of short-range ordered, parallel-stacked graphite crystallites in PC-800-0.5.
The use of the biomass porous carbon material of the present invention is described in detail by example 4.
Example 4
The specific process of this embodiment is as follows: adding the biomass porous carbon prepared in the embodiment 3, namely PC-800-0.5 into a chloramphenicol aqueous solution for oscillation adsorption, filtering to obtain an adsorbed aqueous solution,
the application performance of the biomass porous carbon for removing chloramphenicol from water is evaluated, and the evaluation comprises the following specific steps:
preparing a chloramphenicol solution: dissolving chloramphenicol into deionized water to prepare 100mg/L and 120mg/L chloramphenicol solutions respectively.
(1) PC-800-0.5 at different temperatures to chloramphenicol adsorption data and kinetic model fitting
Respectively measuring 12 groups of 20mL 120mg/L bisphenol A solution, respectively placing the 120mg/L bisphenol A solution into 12 centrifugal tubes, respectively adding 3.0mg of PC-800-0.5 prepared in example 3 into each centrifugal tube, then placing the centrifugal tubes into a constant-temperature water bath oscillator with the temperature of 303K for oscillating adsorption, respectively controlling the oscillating time of 11 centrifugal tubes to be 5min, 10min, 15min, 30min, 45min, 60min, 90min, 120min, 180min, 240min, 300min and 420min, respectively sampling and centrifuging to obtain supernatant, measuring the chloramphenicol concentration in the supernatant, and further calculating the adsorption quantity Qt(mg/g) adsorption quantity Q on the abscissa of the oscillation time t (min)t(mg/g) is the ordinate and adsorption data were fitted using first and second order kinetics-simulated models, the results of which are shown in FIG. 4.
FIG. 4 is a graph of fitting the adsorption kinetics of PC-800-0.5 to chloramphenicol prepared in example 3 of the present invention, and it can be seen from FIG. 4 that the adsorption rate of PC-800-0.5 to chloramphenicol is very fast within 120min from the start of adsorption, and the adsorption amount reaches 95% of the saturated adsorption amount within 120min, while the adsorption rate of PC-800-0.5 to chloramphenicol becomes flat within 120min to 720min, and the adsorption amount slowly reaches equilibrium; meanwhile, as can be seen from the curve in FIG. 4, the curve obtained by fitting the pseudo-second order kinetic model better describes the experimental data, which shows that PC-800-0.5 has the chemical adsorption effect on chloramphenicol and pi-pi EDA interaction exists between the two.
(2) Influence of PC-800-0.5 on chloramphenicol adsorption amount at different pH
Adjusting the pH of 120mg/L chloramphenicol solution by using 0.1mol/L diluted HCl and 0.1mol/L NaOH solution to respectively obtain chloramphenicol solutions with the pH of 2-10; then, 3.0mg of PC-800-0.5 prepared in example 3 was placed in each caseRespectively containing 20mL of chloramphenicol solution with the pH value of 2-10, placing the chloramphenicol solution in a constant-temperature water bath oscillator with the temperature of 303K for oscillation and adsorption for 12h, sampling and centrifuging respectively to obtain supernatant, measuring the chloramphenicol concentration in the supernatant, and calculating the adsorption capacity Qe(mg/g) adsorption Capacity Q on the abscissa of pH of chloramphenicol solutione(mg/g) is plotted on the ordinate as a bar graph, and the results are shown in FIG. 5.
FIG. 5 is a graph showing the adsorption of chloramphenicol by PC-800-0.5 prepared in example 3 of the present invention at different pH values, and it can be seen from FIG. 5 that the adsorption capacity Q is varied with the pH of the chloramphenicol solution ranging from 2 to 10eThe change is small, the influence of pH on the adsorption of chloramphenicol in a water body by PC-800-0.5 is small, and when the pH of a chloramphenicol solution is 2-6, the adsorption capacity QeSlightly increased, and when the pH value of the chloramphenicol solution is 6-10, the adsorption capacity Q iseA slight decrease indicates that the electrostatic interaction between PC-800-0.5 and chloramphenicol and the pi-pi EDA interaction affect the adsorption capacity of PC-800-0.5.
(3) Influence of PC-800-0.5 on chloramphenicol adsorption capacity under different humic acid concentrations
In order to simulate an actual water environment, 1.0mg, 3.0mg, 5.0mg and 7.0mg of humic acid are respectively added into a beaker, 120mg/L of chloramphenicol solution is adopted for dissolving, then the solution is transferred into a 100mL volumetric flask for shaking up and fixing the volume to obtain chloramphenicol solutions with the concentrations of 10mg/L, 30mg/L, 50mg/L and 70mg/L and the concentrations of 120mg/L of chloramphenicol, 3.0mg of PC-800-0.5 prepared in example 3 is respectively placed into centrifugal tubes containing 20mL of the chloramphenicol solutions, then the chloramphenicol solutions are respectively placed into a constant temperature water bath oscillator with the temperature of 303K for oscillating and adsorbing for 12h, then samples are respectively taken and centrifuged to obtain supernatant, the chloramphenicol concentration in the supernatant is measured, and the adsorption capacity Q is calculatede(mg/g), humic acid concentration of chloramphenicol solution as abscissa, adsorption capacity Qe(mg/g) is plotted on the ordinate as a bar graph, and the results are shown in FIG. 6.
FIG. 6 is a graph showing the adsorption of PC-800-0.5 on chloramphenicol under humic acid interference according to example 3 of the present invention, and it can be seen from FIG. 6 that as the concentration of humic acid in chloramphenicol solution increases, the adsorption amount of PC-800-0.5 on chloramphenicol gradually decreases from 616.5mg/g to 567.1mg/g, and the decrease is not significant, and the presence of surface humic acid has an effect on the adsorption capacity of PC-800-0.5 on chloramphenicol, indicating that the competitive adsorption is caused by van der Waals force, hydrogen bonding and π - π EDA interaction between humic acid and chloramphenicol molecules.
(4) Influence of PC-800-0.5 on chloramphenicol adsorption capacity in different metal ion interference environments
Respectively containing 0.01mol of four common metal ions, namely K+、Na+、Ca2+、Mg2+Adding salt into a beaker, dissolving with 100mg/L chloramphenicol solution, transferring into a 100mL volumetric flask, shaking up to constant volume to obtain metal ion concentration K+、Na+、Ca2+、Mg2+Respectively 0.1mol/L of chloramphenicol solution with chloramphenicol concentration of 100mg/L, simultaneously preparing chloramphenicol solution without metal ions and with chloramphenicol concentration of 100mg/L as blank groups, respectively placing 3.0mg of PC-800-0.5 prepared in example 3 into centrifuge tubes containing 20mL of the chloramphenicol solution, respectively placing the centrifuge tubes in a constant temperature water bath oscillator with temperature of 303K for oscillating adsorption for 12h, respectively sampling and centrifuging to obtain supernatant, measuring chloramphenicol concentration in the supernatant, and calculating adsorption capacity Qe(mg/g), the adsorption capacity Q is the abscissa of the metal ion in the chloramphenicol solutione(mg/g) is plotted on the ordinate as a bar graph, and the results are shown in FIG. 7.
FIG. 7 is a graph showing the adsorption of chloramphenicol by PC-800-0.5 prepared in example 3 of the present invention under metal ion interference, and it can be seen from FIG. 7 that monovalent metal ion (K) is present in a high metal ion concentration of 0.1mol/L+，Na+) And divalent metal ion (Ca)2+，Mg2+) Has no influence on the adsorption of PC-800-0.5 to chloramphenicol, which shows that PC-800-0.5 has good metal ion interference resistance.
(5) Influence of PC-800-0.5 desorption regeneration on chloramphenicol adsorption amount
3.0mg of PC-800-0.5 prepared in example 3 of the present invention was placed in a centrifuge tube containing 20mL of 120mg/L chloramphenicol solution, and then placed in a chamber at 303KCarrying out oscillation adsorption in a warm water bath oscillator for 12h, centrifuging to obtain a precipitate, repeating the oscillation adsorption process for multiple times, and collecting the precipitate; then, repeatedly washing with clear water to remove the adsorbed chloramphenicol, and finishing the desorption process; placing the washed precipitate in a beaker containing absolute ethyl alcohol, sealing, magnetically stirring and desorbing for 8h, then performing suction filtration and cleaning by using deionized water, and placing in a drying oven at 105 ℃ for drying to complete the regeneration process to obtain regenerated PC-800-0.5; continuously repeating the oscillating adsorption process, the desorption process and the regeneration process in sequence for the regenerated PC-800-0.5, collecting supernatant obtained by each centrifugation, measuring the concentration of chloramphenicol in the supernatant, and further calculating the adsorption capacity Qe(mg/g), the number of desorption regeneration times of PC-800-0.5 is taken as the abscissa, and the adsorption capacity Qe(mg/g) is plotted on the ordinate as a bar graph, and the results are shown in FIG. 8.
FIG. 8 is a graph showing the desorption regeneration performance of PC-800-0.5 prepared in example 3 of the present invention, and it can be seen from FIG. 8 that the adsorption capacities of 4 desorption regeneration cycles of PC-800-0.5 are 708.7mg/g, 648.0mg/g, 655.6mg/g and 628.2mg/g, respectively, and the decrease amount of the adsorption capacity of PC-800-0.5 is very small as the number of desorption regeneration cycles increases, and the adsorption capacity of PC-800-0.5 after 4 desorption regeneration cycles is 87.3% of the initial adsorption capacity, which indicates that the regeneration performance of PC-800-0.5 is excellent, indicating that chloramphenicol blocks the pore structure of PC-800-0.5 after adsorption, resulting in the decrease of the adsorption removal performance of chloramphenicol.
In conclusion, the biomass porous carbon has great application potential in the aspect of adsorbing and removing chloramphenicol in a water body.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
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