CN115722194B - Nitric acid modified lotus leaf charcoal adsorption material and preparation method and application thereof - Google Patents
Nitric acid modified lotus leaf charcoal adsorption material and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 47
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 239000003463 adsorbent Substances 0.000 claims description 10
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- 238000005119 centrifugation Methods 0.000 claims description 3
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- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 abstract description 12
- 229960004989 tetracycline hydrochloride Drugs 0.000 abstract description 12
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 abstract description 8
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- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 7
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- ORJVQPIHKOARKV-UHFFFAOYSA-N Nuciferine Natural products C1C2=CC=CC=C2C2=C(OC)C(OC)=CC3=C2C1N(C)CC3 ORJVQPIHKOARKV-UHFFFAOYSA-N 0.000 description 2
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Abstract
The invention discloses a nitric acid modified lotus leaf charcoal adsorption material, a preparation method and application thereof, wherein the method comprises the following steps: drying and crushing lotus leaves to obtain lotus leaf powder; calcining the lotus leaf powder to obtain lotus leaf charcoal; adding a nitric acid solution into the nucifera leaf charcoal, and carrying out ultrasonic treatment to obtain a precursor solution; adjusting the pH value of the precursor solution to be neutral, and then performing hydrothermal reaction; and centrifuging and drying the solution after the hydrothermal reaction to obtain the nitric acid modified lotus leaf charcoal adsorption material. The lotus leaf biomass charcoal material prepared by the preparation method provided by the invention has a large specific surface area and rich pore structures, can effectively remove dyes and antibiotics in water, has an adsorption capacity of 151.8mg/g for 5h of methyl orange solution, and has an adsorption capacity of 59.2mg/g for adsorbing tetracycline hydrochloride.
Description
Technical Field
The invention belongs to the technical field of adsorption materials, and particularly relates to a nitric acid modified lotus leaf charcoal adsorption material, and a preparation method and application thereof.
Background
In recent years, insufficiently treated wastewater from textile, leather, pharmaceutical and personal care products (PCPP) industries, etc., may pose a hazard to human health and the natural environment. An increasing number of people have called for sustainable solutions to environmental problems. Biochar is attracting attention as a low-cost material and is used in the fields of carbon sequestration, soil improvement, wastewater treatment, and the like.
Many industrial processes discharge large amounts of dye-containing waste water without effective treatment, and direct discharge poses a threat to the environment because these waste waters are toxic and carcinogenic. Among the various techniques available for treating dye contaminant wastewater, adsorption is the most competitive method because of its many advantages, such as low cost, high efficiency, and ease of operation. Currently, activated carbon is the most commonly used adsorbent. Activated carbon is typically made from coal or petroleum pitch, but is relatively expensive, and researchers have been looking for alternative carbon sources (e.g., biological materials and industrial waste) to produce porous carbon materials with the desired properties, given the cost and availability of resources.
Cellulose is the most abundant natural polysaccharide polymer on earth and has attracted increasing attention in various applications. Natural cellulosic fibers have been used as a carbon source to prepare activated carbon adsorbents for wastewater treatment. Many industries, such as textile, paper and agricultural, produce significant amounts of cellulose-rich waste, which is important for sustainable future conversion to commodity products. For example, fiber adsorbents are prepared from waste textile fibers for heavy metal removal.
As the wastewater adsorbent, biochar is considered As a substitute for Activated Carbon (AC) for removing various pollutants including inorganic anions (NO 3 -,PO4 3-), metal cations (Pb (II), as (III), and Cd (II)), organic dyes (methyl orange, rhodamine B), and the like. However, the relatively low surface area of biochar and the effects of abiotic and/or biological processes may limit its effectiveness in certain applications. Therefore, the modification of the biochar and the improvement of the adsorption performance thereof have profound research significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the nitric acid modified lotus leaf charcoal adsorption material, and the preparation method and the application thereof.
In order to achieve the above purpose, the present invention is realized by the following technical scheme:
the invention provides a preparation method of a nitric acid modified lotus leaf charcoal adsorption material, which comprises the following steps:
(1) Drying and crushing lotus leaves to obtain lotus leaf powder;
(2) Calcining lotus leaf powder to obtain lotus leaf charcoal;
(3) Adding a nitric acid solution into lotus leaf charcoal, and performing ultrasonic treatment to obtain a precursor solution;
(4) After the pH value of the precursor solution is adjusted to be neutral, carrying out hydrothermal reaction;
(5) And centrifuging and drying the solution after the hydrothermal reaction to obtain the nitric acid modified lotus leaf charcoal adsorption material.
Preferably, in step (1), the temperature of the drying is 70 ℃.
Preferably, in the step (2), the conditions for calcination are: calcining is carried out under the nitrogen atmosphere, the calcining temperature is 800 ℃, the heating rate is 5 ℃/min, and the calcining time is 2h.
The nitric acid used in the invention is dilute nitric acid, and preferably, in the step (3), the concentration of the nitric acid is 1mol/L.
Preferably, in the step (3), the mass ratio of the nuciferine carbon to the nitric acid is 1 (6-10), the ultrasonic time is 30-120 min, and the ultrasonic frequency is 40kHz. The mass ratio of the lotus leaf charcoal to the nitric acid can be 1:6,1:8,1:9 and 1:10; the ultrasonic time may be 30min,40min,50min,60min,70min,80min,90min,100min or 120min.
More preferably, the mass ratio of the nucifera leaf charcoal to the nitric acid is 1:8, the ultrasonic time is 90min, and the ultrasonic frequency is 40kHz.
Preferably, in the step (4), the temperature of the hydrothermal reaction is 160 ℃, and the reaction time is 24 hours.
Preferably, in step (5), the centrifugation is carried out at 4000r/min and the drying temperature is 70 ℃.
The invention also provides the nitric acid modified lotus leaf charcoal adsorption material prepared by the preparation method.
The invention also provides application of the nitric acid modified lotus leaf charcoal adsorption material prepared by the preparation method in removing dyes and/or antibiotics in water.
The beneficial effects of the invention are as follows:
According to the invention, lotus leaves are used as a carbon source, the lotus leaf biomass charcoal is generated after calcination, the specific surface area of the biochar is controlled by changing the dosage of the lotus leaf biomass charcoal and the ultrasonic time, and then pore expansion and pore forming are further carried out through hydrothermal reaction, so that the pore structure is increased, and the adsorption effect is improved.
The biomass material has wide sources, low acquisition cost and repeated use, saves resources and does not pollute the environment, and is a green material. The biomass charcoal material prepared by the preparation method provided by the invention has a large specific surface area and rich pore structures, can effectively remove dyes and antibiotics in water, has an adsorption capacity of 151.8mg/g in 5h of methyl orange solution adsorption, and has an adsorption capacity of 59.2mg/g of tetracycline hydrochloride adsorption.
Drawings
In order to more clearly illustrate the technical solution of the embodiments of the present invention, the drawings of the embodiments will be briefly described below.
FIG. 1 is an X-ray diffraction pattern of the activated carbon material prepared in example 5 and comparative example 1 of the present invention.
FIG. 2 is a scanning electron microscope image of the activated carbon materials prepared in example 5 and comparative example 1 of the present invention; wherein fig. 2 (a) is a scanning electron microscope image of the activated carbon material prepared in comparative example 1, and fig. 2 (b) is a scanning electron microscope image of the activated carbon material prepared in example 5.
FIG. 3 is a graph showing the adsorption performance of the methyl orange adsorption solutions of examples 1 to 6 and comparative example 1 according to the present invention.
FIG. 4 is a graph showing adsorption performance of the tetracycline hydrochloride solutions of examples 1 to 6 and comparative example 1 of the present invention.
FIG. 5 is an adsorption isothermal curve of the present invention for examples 1 to 6 and comparative example 1 for adsorbing methyl orange solutions of different concentrations.
FIG. 6 is an adsorption isothermal curve of the tetracycline hydrochloride solutions of different concentrations according to examples 1 to 6 and comparative example 1 of the present invention.
FIG. 7 is a graph showing the desorption of nitrogen and the pore size distribution in example 1 of the present invention.
FIG. 8 is a graph showing the desorption of nitrogen and the pore size distribution in example 2 of the present invention.
FIG. 9 is a graph showing the desorption of nitrogen and the pore size distribution in example 3 of the present invention.
FIG. 10 is a graph showing the desorption of nitrogen and the pore size distribution in example 4 of the present invention.
FIG. 11 is a graph showing the desorption of nitrogen and the pore size distribution in example 5 of the present invention.
FIG. 12 is a graph showing the desorption of nitrogen and the pore size distribution in example 6 of the present invention.
FIG. 13 is a graph showing the desorption of nitrogen gas and the pore size distribution of comparative example 1 of the present invention.
FIG. 14 is a graph showing the adsorption performance of the methyl orange solution 5h of example 5 and comparative example 2 of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
Example 1
Cleaning picked lotus leaves, placing the lotus leaves under the sun, airing moisture, crushing and collecting the sun-dried parts of the sun-dried lotus leaves by hands, kneading the sun-dried lotus leaves as far as possible by hands, putting the sun-dried lotus leaves into a baking oven, and further baking the lotus leaves for 24 hours at 70 ℃ to ensure that the moisture of the lotus leaves is sufficiently baked; then the dried lotus leaves are put into an XFB-200 high-speed traditional Chinese medicine pulverizer in batches for pulverization, the pulverized lotus leaves are put into a tube furnace which is filled with N 2 for calcination, the calcination condition is 800 ℃, the heating rate is 5 ℃/min, and the lotus leaf charcoal (BC) is obtained after heat preservation for 2 hours; and grinding the lotus leaf charcoal by using a mortar, and filling the ground lotus leaf charcoal into a sealing bag. Putting 0.42g of lotus leaf carbon powder into a 100mL beaker, adding 40mL of 1mol/L HNO 3 solution, carrying out ultrasonic treatment for 30min, adjusting the pH value to be neutral by ammonia water after ultrasonic treatment is finished, transferring the solution into a 100mL polytetrafluoroethylene reaction kettle liner, putting the kettle liner into a baking oven for hydrothermal reaction, carrying out centrifugal cleaning after the hydrothermal reaction is finished, carrying out centrifugal cleaning at the rotating speed of 4000r/min, putting the kettle liner into the baking oven for drying at 70 ℃, and grinding by a mortar after the drying is finished to obtain the NBC-6-30 lotus leaf carbon adsorption material.
Example 2
Cleaning picked lotus leaves, placing the lotus leaves under the sun, airing moisture, crushing and collecting the sun-dried parts of the sun-dried lotus leaves by hands, kneading the sun-dried lotus leaves as far as possible by hands, putting the sun-dried lotus leaves into a baking oven, and further baking the lotus leaves for 24 hours at 70 ℃ to ensure that the moisture of the lotus leaves is sufficiently baked; then the dried lotus leaves are put into an XFB-200 high-speed traditional Chinese medicine pulverizer in batches for pulverization, the pulverized lotus leaves are put into a tube furnace which is filled with N 2 for calcination, the calcination condition is 800 ℃, the heating rate is 5 ℃/min, and the lotus leaf charcoal (BC) is obtained after heat preservation for 2 hours; and grinding the lotus leaf charcoal by using a mortar, and filling the ground lotus leaf charcoal into a sealing bag. Putting 0.315g of lotus leaf carbon powder into a 100mL beaker, adding 40mL of 1mol/L HNO 3 solution, carrying out ultrasonic treatment for 30min, adjusting the pH value to be neutral by ammonia water after ultrasonic treatment is finished, transferring the solution into a 100mL polytetrafluoroethylene reaction kettle liner, putting the kettle liner into an oven for hydrothermal reaction, carrying out centrifugal cleaning after the hydrothermal reaction is finished, carrying out centrifugal cleaning at the speed of 4000r/min, putting the kettle liner into the oven for drying at 70 ℃, and grinding by a mortar after the drying is finished to obtain the NBC-8-30 lotus leaf carbon adsorption material.
Example 3
Cleaning picked lotus leaves, placing the lotus leaves under the sun, airing moisture, crushing and collecting the sun-dried parts of the sun-dried lotus leaves by hands, kneading the sun-dried lotus leaves as far as possible by hands, putting the sun-dried lotus leaves into a baking oven, and further baking the lotus leaves for 24 hours at 70 ℃ to ensure that the moisture of the lotus leaves is sufficiently baked; then the dried lotus leaves are put into an XFB-200 high-speed traditional Chinese medicine pulverizer in batches for pulverization, the pulverized lotus leaves are put into a tube furnace which is filled with N 2 for calcination, the calcination condition is 800 ℃, the heating rate is 5 ℃/min, and the lotus leaf charcoal (BC) is obtained after heat preservation for 2 hours; and grinding the lotus leaf charcoal by using a mortar, and filling the ground lotus leaf charcoal into a sealing bag. Putting 0.252g of lotus leaf carbon powder into a 100mL beaker, adding 40mL of 1mol/L HNO 3 solution, carrying out ultrasonic treatment for 30min, adjusting the pH value to be neutral by ammonia water after ultrasonic treatment is finished, transferring into a 100mL polytetrafluoroethylene reaction kettle liner, putting into a baking oven for hydrothermal reaction, carrying out centrifugal cleaning after the hydrothermal reaction is finished, carrying out centrifugal cleaning at the rotating speed of 4000r/min, putting into the baking oven, drying at 70 ℃, and grinding by a mortar after the drying is finished to obtain the NBC-10-30 lotus leaf carbon adsorption material.
Example 4
Cleaning picked lotus leaves, placing the lotus leaves under the sun, airing moisture, crushing and collecting the sun-dried parts of the sun-dried lotus leaves by hands, kneading the sun-dried lotus leaves as far as possible by hands, putting the sun-dried lotus leaves into a baking oven, and further baking the lotus leaves for 24 hours at 70 ℃ to ensure that the moisture of the lotus leaves is sufficiently baked; then the dried lotus leaves are put into an XFB-200 high-speed traditional Chinese medicine pulverizer in batches for pulverization, the pulverized lotus leaves are put into a tube furnace which is filled with N 2 for calcination, the calcination condition is 800 ℃, the heating rate is 5 ℃/min, and the lotus leaf charcoal (BC) is obtained after heat preservation for 2 hours; and grinding the lotus leaf charcoal by using a mortar, and filling the ground lotus leaf charcoal into a sealing bag. Putting 0.315g of lotus leaf carbon powder into a 100mL beaker, adding 40mL of 1mol/L HNO 3 solution, carrying out ultrasonic treatment for 60min, adjusting the pH value to be neutral by ammonia water after ultrasonic treatment is finished, transferring the solution into a 100mL polytetrafluoroethylene reaction kettle liner, putting the kettle liner into an oven for hydrothermal reaction, carrying out centrifugal cleaning after the hydrothermal reaction is finished, carrying out centrifugal cleaning at the speed of 4000r/min, putting the kettle liner into the oven for drying at 70 ℃, and grinding by a mortar after the drying is finished to obtain the NBC-8-60 lotus leaf carbon adsorption material.
Example 5
Cleaning picked lotus leaves, placing the lotus leaves under the sun, airing moisture, crushing and collecting the sun-dried parts of the sun-dried lotus leaves by hands, kneading the sun-dried lotus leaves as far as possible by hands, putting the sun-dried lotus leaves into a baking oven, and further baking the lotus leaves for 24 hours at 70 ℃ to ensure that the moisture of the lotus leaves is sufficiently baked; then the dried lotus leaves are put into an XFB-200 high-speed traditional Chinese medicine pulverizer in batches for pulverization, the pulverized lotus leaves are put into a tube furnace which is filled with N 2 for calcination, the calcination condition is 800 ℃, the heating rate is 5 ℃/min, and the lotus leaf charcoal (BC) is obtained after heat preservation for 2 hours; and grinding the lotus leaf charcoal by using a mortar, and filling the ground lotus leaf charcoal into a sealing bag. Putting 0.315g of lotus leaf carbon powder into a 100mL beaker, adding 40mL of 1mol/L HNO 3 solution, carrying out ultrasonic treatment for 90min, adjusting the pH value to be neutral by ammonia water after ultrasonic treatment is finished, transferring the solution into a 100mL polytetrafluoroethylene reaction kettle liner, putting the kettle liner into an oven for hydrothermal reaction, carrying out centrifugal cleaning after the hydrothermal reaction is finished, carrying out centrifugal cleaning at the speed of 4000r/min, putting the kettle liner into the oven for drying at 70 ℃, and grinding by a mortar after the drying is finished to obtain the NBC-8-90 lotus leaf carbon adsorption material.
Example 6
Cleaning picked lotus leaves, placing the lotus leaves under the sun, airing moisture, crushing and collecting the sun-dried parts of the sun-dried lotus leaves by hands, kneading the sun-dried lotus leaves as far as possible by hands, putting the sun-dried lotus leaves into a baking oven, and further baking the lotus leaves for 24 hours at 70 ℃ to ensure that the moisture of the lotus leaves is sufficiently baked; then the dried lotus leaves are put into an XFB-200 high-speed traditional Chinese medicine pulverizer in batches for pulverization, the pulverized lotus leaves are put into a tube furnace which is filled with N 2 for calcination, the calcination condition is 800 ℃, the heating rate is 5 ℃/min, and the lotus leaf charcoal (BC) is obtained after heat preservation for 2 hours; and grinding the lotus leaf charcoal by using a mortar, and filling the ground lotus leaf charcoal into a sealing bag. Putting 0.315g of lotus leaf carbon powder into a 100mL beaker, adding 40mL of 1mol/L HNO 3 solution, carrying out ultrasonic treatment for 120min, adjusting the pH value to be neutral by ammonia water after ultrasonic treatment is finished, transferring the solution into a 100mL polytetrafluoroethylene reaction kettle liner, putting the kettle liner into an oven for hydrothermal reaction, carrying out centrifugal cleaning after the hydrothermal reaction is finished, carrying out centrifugal cleaning at the rotating speed of 4000r/min, putting the kettle liner into the oven for drying at 70 ℃, and grinding by a mortar after the drying is finished to obtain the NBC-8-120 lotus leaf carbon adsorption material.
Comparative example 1
Cleaning picked lotus leaves, sun-drying the lotus leaves in the sun, crushing and collecting sun-dried parts of the sun-dried lotus leaves by hands, crushing the sun-dried lotus leaves by hands as far as possible, putting the sun-dried lotus leaves into a baking oven, further baking the sun-dried lotus leaves at 70 ℃ for 24 hours to ensure that the moisture of the lotus leaves is sufficiently baked, putting the baked lotus leaves into an XFB-200 high-speed traditional Chinese medicine pulverizer in batches to crush the lotus leaves, putting the crushed lotus leaves into a tube furnace which is filled with N 2 for calcination, wherein the calcination condition is 800 ℃, the heating rate is 5 ℃/min, and preserving the heat for 2 hours to obtain lotus leaf charcoal (BC), and grinding the lotus leaf charcoal by using a mortar to obtain original lotus leaf charcoal.
Comparative example 2
Nitric acid-modified, nuciferous carbon adsorbent material was prepared in the same manner as in example 5, except that the hydrothermal reaction was not performed.
[ Performance test ]
1. X-ray diffraction experiment
Fig. 1 is an X-ray diffraction pattern of example 5 and comparative example 1, and it can be seen from fig. 1 that a broad peak at 2θ=24.8° and 2θ=42.9° can be found in example 5, indicating that the nitric acid-modified nuciferous carbon material prepared according to the present invention mainly contains a large amount of amorphous carbon, whereas the peak generated in comparative example 1 is formed by a substance contained in biomass itself.
2. SEM scan
In fig. 2, (a) is a scanning electron microscope image of the activated carbon material prepared in comparative example 1, and (b) is a scanning electron microscope image of the activated carbon material prepared in example 5, it can be seen by comparison that the lotus leaf carbon material is formed by stacking larger blocky particles before being activated by nitric acid, but the NBC-8-90 activated carbon material after being activated by nitric acid and subjected to hydrothermal reaction can obviously show that the particle size is reduced, and a mesoporous structure is formed, which is favorable for the entry and adsorption of pollutants in pores, thereby improving the adsorption effect.
3. Adsorption Performance test
3.1 Preparing 40mg/L methyl orange solution and 40mg/L tetracycline hydrochloride solution respectively, adding 100mL of prepared methyl orange solution or tetracycline hydrochloride solution into a 150mL conical flask, adding 20mg of biomass adsorbent, performing fixed-point measurement on adsorption effect, and performing the measurement on each group of examples and comparative examples to obtain 5h adsorption amounts of two pollutants in table 1 and adsorption curves of fig. 3 and 4.
TABLE 1
It is apparent from Table 1 that the specific surface area of the adsorbent prepared in the examples of the present invention is larger, and the adsorption amounts to methyl orange and tetracycline hydrochloride are larger. The ratio of lotus leaf charcoal to nitric acid molecular mass is 1:8, because the nitric acid activation process leaves a pore size on the biomass, and the mass ratio is 1: at 6, the nitric acid is relatively less, the activation is incomplete, and the mesoporous space is generated, wherein the mass ratio is 1: at 10, nitric acid is relatively more, and activation is excessive, so that mesopores are connected to form macropores, and the specific surface area is reduced, thus 1:8 is the optimal ratio, and the obtained specific surface area is the largest.
Fig. 3 shows adsorption performance graphs of the biomass charcoal materials prepared in examples 1 to 6 and comparative example 1 for adsorbing methyl orange solution 5h, and it can be observed that all the examples have different degrees of performance improvement relative to comparative example 1, and the effect of example 5 is most obvious, which is attributed to that the lotus leaf charcoal is fully activated by longer ultrasonic time, the specific surface area is increased, solute molecules are more favorably introduced into the pore structure of the activated carbon, the adsorption capacity is improved, and the effect of example 6 is not better than that of example 5 because part of mesopores collapse and become macropores due to overlong activation time, the specific surface area is reduced, and adsorption sites are reduced, so that the adsorption effect is reduced. The adsorption effect of examples 1 to 6 is superior to that of comparative example 1, because nitric acid is used to activate the nuciferine carbon after the nucife carbon is modified, a large amount of mesoporous structures are generated, and the specific surface area is increased.
Fig. 4 shows the adsorption performance of the biomass charcoal materials prepared in examples 1 to 6 and comparative example 1 for adsorbing tetracycline hydrochloride solution for 5 hours. The adsorption effect of all the examples is similar to the trend of fig. 3, which shows that the biomass adsorption material prepared by the method has a certain adsorption effect on different types of pollutants in water and has good applicability.
3.2 Preparing 7 groups of methyl orange solution and tetracycline hydrochloride solution (20, 30, 40, 50, 60, 70 and 80 mg/L) with different concentrations respectively, placing 150mL of each group into different conical flasks, adding 20mg of biomass adsorbents prepared in examples 1-6 and comparative example 1 into each group, continuously reacting for 24 hours at room temperature by using a constant-temperature oscillator, taking out the solution for centrifugation operation, taking clear solution on a centrifuge tube, respectively measuring the absorbance of methyl orange and tetracycline hydrochloride after adsorption by using UV-Vis, and calculating the corresponding adsorption amount, wherein the adsorption diagram is shown in figures 5 and 6.
Fig. 5 and 6 are graphs showing the effect of adsorbing solutions of methyl orange and tetracycline hydrochloride in different concentrations in examples 1 to 6 and comparative example 1, respectively, and the adsorption curves were subjected to Langmuir and Freundlich fitting, and it can be seen from the graphs that the adsorption effect of the embodiment of the present invention for adsorbing methyl orange and tetracycline hydrochloride in different concentrations is better than that in comparative example 1, indicating that the adsorption effect is structurally related to the adsorbent itself, is not affected by the concentration of dye or antibiotic, and that the adsorption process is found to be suitable for Langmuir adsorption isotherms.
Fig. 7 to 13 are graphs of nitrogen adsorption and desorption curves and pore size distribution diagrams of example 1, example 2, example 3, example 4, example 5, example 6 and comparative example 1, respectively, from which specific surface areas of different examples were calculated by BET equation, and the results are shown in table 1. It can be seen that NBC-8-90 has the largest specific surface area, up to 641.7m 2/g, corresponding to the experimental results of FIGS. 3-4, indicating that the larger specific surface area is more advantageous for the improvement of adsorption effect.
Fig. 14 is a graph showing the 5h adsorption effect of the methyl orange solution of example 5 and comparative example 2, and it is obvious that the adsorption effect of the hydrothermal sample is greater than that of the non-hydrothermal sample, because the hydrothermal sample provides high-temperature and high-pressure environment for the sample, and the hole expansion and pore formation are performed by the CO 2 and water contained in the lotus leaf biochar, so as to achieve the effect of increasing the specific surface area. The hydrothermal temperature can enable the pressure in the reaction kettle to change, and the pressure in the reaction kettle and the hydrothermal time can enable the reaming and pore-forming effects of CO 2 and water to change.
It should be noted that, the foregoing embodiments all belong to the same inventive concept, and the descriptions of the embodiments have emphasis, and where the descriptions of the individual embodiments are not exhaustive, reference may be made to the descriptions of the other embodiments.
The foregoing examples merely illustrate embodiments of the invention and are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (9)
1. The preparation method of the nitric acid modified nucifera leaf charcoal adsorption material is characterized by comprising the following steps of:
(1) Drying and crushing lotus leaves to obtain lotus leaf powder;
(2) Calcining the lotus leaf powder to obtain lotus leaf charcoal;
(3) Adding a nitric acid solution into the nucifera leaf charcoal, and carrying out ultrasonic treatment to obtain a precursor solution;
(4) Adjusting the pH value of the precursor solution to be neutral, and then performing hydrothermal reaction;
(5) Centrifuging and drying the solution after the hydrothermal reaction to obtain a nitric acid modified lotus leaf charcoal adsorption material;
in the step (3), the mass ratio of the lotus leaf charcoal to the nitric acid is 1 (6-10), the ultrasonic time is 30-120 min, and the ultrasonic frequency is 40 kHz.
2. A method for preparing a nitric acid modified nucifera leaf char adsorption material according to claim 1, wherein in step (1), the temperature of said drying is 70 ℃.
3. A method for preparing a nitric acid modified nucifera leaf char adsorption material according to claim 1, wherein in step (2), the calcination conditions are: calcining under nitrogen atmosphere, wherein the calcining temperature is 800 ℃, the heating rate is 5 ℃/min, and the calcining time is 2 h.
4. A method for producing a nitric acid-modified, nucifera leaf char adsorption material according to claim 1, wherein in step (3), the concentration of the nitric acid solution is 1 mol/L.
5. A method for preparing a nitric acid modified nucifera leaf charcoal adsorption material according to claim 1, wherein in step (3), the mass ratio of nucifera leaf charcoal to nitric acid is 1:8, the ultrasonic time is 90 min, and the ultrasonic frequency is 40 kHz.
6. A method for preparing a nitric acid modified nucifera leaf charcoal adsorption material according to claim 1, wherein in step (4), the hydrothermal reaction temperature is 160 ℃, and the reaction time is 24 h.
7. A method for preparing a nitric acid modified nucifera leaf char adsorption material according to claim 1, wherein in step (5), centrifugation is performed at 4000 r/min, and the drying temperature is 70 ℃.
8. A nitric acid modified, nuciferous carbon adsorbent material prepared according to the method of any one of claims 1-7.
9. Use of a nitric acid modified nucifera leaf charcoal adsorption material prepared by a preparation method according to any one of claims 1-7 for removing dyes and/or antibiotics from water.
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