CN111675205A - Preparation method of zinc oxide-assisted nitrogen-doped biomass charcoal - Google Patents
Preparation method of zinc oxide-assisted nitrogen-doped biomass charcoal Download PDFInfo
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- CN111675205A CN111675205A CN202010408558.9A CN202010408558A CN111675205A CN 111675205 A CN111675205 A CN 111675205A CN 202010408558 A CN202010408558 A CN 202010408558A CN 111675205 A CN111675205 A CN 111675205A
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000002028 Biomass Substances 0.000 title claims abstract description 68
- 239000003610 charcoal Substances 0.000 title claims abstract description 57
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 45
- 229920001661 Chitosan Polymers 0.000 claims abstract description 38
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004246 zinc acetate Substances 0.000 claims abstract description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 238000002791 soaking Methods 0.000 claims abstract description 13
- 229960000583 acetic acid Drugs 0.000 claims abstract description 11
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 8
- 238000004108 freeze drying Methods 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 239000003242 anti bacterial agent Substances 0.000 abstract description 13
- 229940088710 antibiotic agent Drugs 0.000 abstract description 13
- 238000001179 sorption measurement Methods 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000003115 biocidal effect Effects 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 4
- 239000003575 carbonaceous material Substances 0.000 abstract description 3
- 239000005447 environmental material Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000238424 Crustacea Species 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- GSDSWSVVBLHKDQ-JTQLQIEISA-N Levofloxacin Chemical compound C([C@@H](N1C2=C(C(C(C(O)=O)=C1)=O)C=C1F)C)OC2=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-JTQLQIEISA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 229960003022 amoxicillin Drugs 0.000 description 1
- LSQZJLSUYDQPKJ-NJBDSQKTSA-N amoxicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(O)=O)(C)C)=CC=C(O)C=C1 LSQZJLSUYDQPKJ-NJBDSQKTSA-N 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- CYDMQBQPVICBEU-UHFFFAOYSA-N chlorotetracycline Natural products C1=CC(Cl)=C2C(O)(C)C3CC4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-UHFFFAOYSA-N 0.000 description 1
- 229960004475 chlortetracycline Drugs 0.000 description 1
- CYDMQBQPVICBEU-XRNKAMNCSA-N chlortetracycline Chemical compound C1=CC(Cl)=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-XRNKAMNCSA-N 0.000 description 1
- 235000019365 chlortetracycline Nutrition 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 229960003376 levofloxacin Drugs 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- LSQZJLSUYDQPKJ-UHFFFAOYSA-N p-Hydroxyampicillin Natural products O=C1N2C(C(O)=O)C(C)(C)SC2C1NC(=O)C(N)C1=CC=C(O)C=C1 LSQZJLSUYDQPKJ-UHFFFAOYSA-N 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
Abstract
A preparation method of zinc oxide-assisted nitrogen-doped biomass charcoal. The invention belongs to the technical field of environmental materials. The invention aims to solve the problems that the carbon material prepared by taking single chitosan as a raw material at present is not rich in pore structure and low in adsorption performance of antibiotic wastewater. The method comprises the following steps: firstly, adding chitosan into a glacial acetic acid solution to prepare a chitosan solution; dropwise adding the chitosan solution into the zinc acetate solution, and adjusting the pH value after the dropwise adding is finished; thirdly, carrying out hydrothermal reaction on the mixed solution, and freeze-drying to obtain a chitosan and ZnO conjugate; and fourthly, calcining, soaking in a potassium hydroxide solution, calcining again after soaking, standing in hydrochloric acid, washing with distilled water, and drying to obtain the zinc oxide auxiliary nitrogen-doped biomass charcoal. The method has the advantages of easy operation, low equipment requirement and low production cost, and is suitable for industrial production. The adsorption performance is excellent, and the highest removal rate of the antibiotics is nearly 99 percent.
Description
Technical Field
The invention belongs to the technical field of environmental materials, and particularly relates to a preparation method of zinc oxide-assisted nitrogen-doped biomass charcoal.
Background
Since the clinical use of penicillin, the variety of antibiotics has been increasing, and antibiotics have been widely used in the medical pharmacy, animal husbandry, and aquaculture industries. However, a large amount of antibiotics are discharged into the environment in the form of metabolites and even in the original state, which not only destroy the ecological environment, but also cause drug resistance of bacteria, and may generate certain toxicity to some organisms, and finally threaten the health of human beings.
With respect to this new contaminant, antibiotics, various methods including adsorption methods have been sought by many researchers to remove the antibiotic contaminants from water. In adsorption studies, a porous carbon material is favored, and among them, the use of biomass charcoal is more advantageous: (1) the raw materials for preparing the biomass charcoal are low in price and can be obtained continuously; (2) the biomass charcoal has a repairing effect on soil and has good environmental compatibility; (3) the biomass charcoal material has abundant functional groups on the surface, which is beneficial to improving the adsorption performance.
The chitosan has the characteristics of biocompatibility, biodegradability, immunity enhancement, almost no toxicity and the like, can be continuously obtained from the crustacean solid waste, and is a nitrogen-containing biomass material capable of being continuously developed. Related researches show that nitrogen can endow biomass charcoal with rich surface structure, and improve performances of the biomass charcoal in various aspects such as adsorption, catalysis, energy storage, nitrogen supply of plants and the like. In the field of adsorption, chitosan containing nitrogen elements and carbon elements is selected as a precursor, so that the method is the best choice for preparing nitrogen-doped biomass carbon.
At present, the chitosan is used as a raw material to prepare the biomass charcoal, and excellent performance is shown. However, the biomass charcoal prepared only from chitosan is not very rich in pore structure, and the adsorption performance needs to be further improved. Therefore, finding a suitable raw material to assist chitosan in preparing the porous nitrogen-doped biomass charcoal material so as to improve the removal rate of antibiotics is a topic of extensive attention at present.
Disclosure of Invention
The invention aims to solve the technical problems that the carbon material prepared by taking single chitosan as a raw material at present is not rich in pore structure and low in adsorption performance to antibiotic wastewater, and provides a preparation method of zinc oxide-assisted nitrogen-doped biomass carbon.
The preparation method of the zinc oxide-assisted nitrogen-doped biomass charcoal comprises the following steps:
firstly, adding chitosan into a glacial acetic acid solution for dissolving to prepare a chitosan solution;
dropwise adding the chitosan solution obtained in the step one into a zinc acetate solution, adjusting the pH value to 9-12 by using a sodium hydroxide solution after the dropwise addition is finished, and uniformly stirring to obtain a mixed solution; the volume ratio of the chitosan solution obtained in the step one to the zinc acetate solution is 3: (1-3);
thirdly, carrying out hydrothermal reaction on the mixed solution obtained in the second step, and then carrying out freeze drying to obtain a chitosan and ZnO combined material;
fourthly, firstly calcining the chitosan and ZnO combination obtained in the third step, then soaking the combination in a potassium hydroxide solution, then carrying out secondary calcining treatment after soaking, then standing the combination in hydrochloric acid, washing the combination with distilled water for 3-5 times after standing, and finally drying the combination at the temperature of 60-100 ℃ to obtain the zinc oxide auxiliary nitrogen-doped biomass carbon.
Further limiting, in the first step, the ratio of the mass of the chitosan to the volume of the glacial acetic acid solution is (0.01-0.03) g: 1 mL.
Further limiting, in the first step, the ratio of the mass of the chitosan to the volume of the glacial acetic acid solution is 0.017 g: 1 mL.
Further limiting, the volume concentration of the glacial acetic acid solution in the step one is 1-3%.
Further limiting, in the second step, the volume ratio of the chitosan solution obtained in the first step to the zinc acetate solution is 3: 2.
further limiting, the concentration of the zinc acetate solution in the second step is 0.03 g/mL-0.15 g/mL.
Further limiting, the concentration of the zinc acetate solution in step two is 0.075 g/mL.
Further limiting, the concentration of the sodium hydroxide solution in the step two is 2 mol/L-5 mol/L.
Further limiting, the rotation speed of the stirring in the step two is 500 rpm-700 rpm.
Further limiting, the hydrothermal reaction parameters in the third step are as follows: the temperature is 80-150 ℃, and the time is 6-10 h.
Further limiting, the hydrothermal reaction parameters in the third step are as follows: the temperature is 100 ℃ and the time is 8 h.
Further limiting, the freeze-drying treatment parameters in step three are as follows: the temperature is-70 to-90 ℃, and the time is 65 to 80 hours.
Further limiting, the freeze-drying treatment parameters in step three are as follows: the temperature is-80 ℃ and the time is 72 h.
Further limiting, the primary calcination treatment process in the fourth step specifically comprises: under the protection of nitrogen atmosphere, heating from room temperature to 650-750 ℃ at the heating rate of 3-10 ℃/min, and then preserving heat for 3-5 h at the temperature.
Further limiting, the primary calcination treatment process in the fourth step specifically comprises: heating the mixture from room temperature to 700 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen atmosphere, and then keeping the temperature for 4 h.
Further limiting, the mass concentration of the potassium hydroxide solution in the step four is 4-6%, and the soaking time is 10-14 h.
Further limiting, in the fourth step, the mass concentration of the potassium hydroxide solution is 5%, and the soaking time is 12 hours.
Further limiting, the secondary calcination treatment process in the fourth step is as follows: under the protection of nitrogen atmosphere, heating from room temperature to 700-800 ℃ at a heating rate of 3-10 ℃/min, and then preserving heat for 1-3 h at the temperature.
Further limiting, the secondary calcination treatment process in the fourth step is as follows: heating the mixture from room temperature to 750 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen atmosphere, and then keeping the temperature for 2 h.
Further limiting, the volume concentration of the hydrochloric acid in the step four is 20-30%, and the standing time is 10-14 h.
Further limiting, the volume concentration of the hydrochloric acid in the step four is 25%, and the standing time is 12 h.
Compared with the prior art, the invention has the remarkable effects as follows:
the method has the advantages of easy operation, low equipment requirement, cheap and easily-obtained raw materials such as chitosan, ethanol and the like, low production cost and suitability for industrial production.
The chitosan used in the method is a natural biomass material, and is green and environment-friendly.
The specific surface area of the zinc oxide auxiliary nitrogen-doped biomass charcoal obtained by the method can reach 498.77m2The specific surface area of the nitrogen-doped biomass charcoal is increased by about 75% compared with that of the nitrogen-doped biomass charcoal without zinc acetate.
The zinc oxide auxiliary nitrogen-doped biomass charcoal obtained by the method has a structure similar to a micropore, and the proportion of the micropore structure is about 76%.
The maximum saturated adsorption capacity of the zinc oxide auxiliary nitrogen-doped biomass charcoal obtained by the method disclosed by the invention on antibiotics can reach 533.49 mg/g.
The zinc oxide obtained by the method provided by the invention has excellent adsorption performance for nitrogen-doped biomass carbon, and the highest removal rate of antibiotics is nearly 99%.
Drawings
Fig. 1 is an SEM photograph of zinc oxide-assisted nitrogen-doped biomass charcoal obtained in the first embodiment;
FIG. 2 is an XRD spectrum of zinc oxide assisted nitrogen doped biomass charcoal obtained in the first embodiment;
FIG. 3 is an XPS survey of zinc oxide assisted nitrogen doped biomass charcoal obtained in accordance with a first embodiment;
fig. 4 is an XPS spectrum of zinc oxide-assisted nitrogen-doped biomass charcoal C1s obtained in the first embodiment;
fig. 5 is an XPS spectrum of zinc oxide-assisted nitrogen-doped biomass charcoal N1s obtained in the first embodiment;
FIG. 6 is an XPS spectrum of zinc oxide-assisted nitrogen-doped biochar O1s obtained in the first embodiment;
fig. 7 is an SEM photograph of zinc oxide-assisted nitrogen-doped biomass charcoal obtained in the second embodiment;
fig. 8 is a bar graph of the removal rates of three antibiotics by the zinc oxide-assisted nitrogen-doped biomass charcoal obtained in the first and second embodiments and by the nitrogen-doped biomass charcoal without zinc acetate obtained in the comparative example.
Detailed Description
The first embodiment is as follows: the preparation method of the zinc oxide-assisted nitrogen-doped biomass charcoal comprises the following steps:
firstly, adding chitosan into a glacial acetic acid solution for dissolving to prepare a chitosan solution; the ratio of the mass of the chitosan to the volume of the glacial acetic acid solution is 0.017 g: 1 mL; the volume concentration of the glacial acetic acid solution is 1%;
secondly, dropwise adding 30mL of the chitosan solution obtained in the first step into 20mL of zinc acetate solution with the concentration of 0.075g/mL, adjusting the pH value to 12 by using 2mol/L sodium hydroxide solution after the dropwise addition is finished, and uniformly stirring at the rotating speed of 600rpm to obtain a mixed solution;
thirdly, carrying out hydrothermal reaction on the mixed solution obtained in the second step for 8 hours at the temperature of 100 ℃, and then carrying out freeze drying for 72 hours at the temperature of minus 80 ℃ to obtain a conjugate of chitosan and ZnO;
fourthly, firstly calcining the chitosan and ZnO combination obtained in the third step, then soaking for 12 hours in 5% by mass potassium hydroxide solution, then carrying out secondary calcining treatment after soaking, then standing for 12 hours in 25% by volume hydrochloric acid, washing for 5 times with distilled water after standing, and finally drying at 80 ℃ to obtain the zinc oxide auxiliary nitrogen-doped biomass charcoal; the primary calcination treatment process specifically comprises the following steps: under the protection of nitrogen atmosphere, heating from room temperature to 700 ℃ at the heating rate of 5 ℃/min, and then preserving heat for 4h at the temperature; the secondary calcination treatment process comprises the following steps: heating the mixture from room temperature to 750 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen atmosphere, and then keeping the temperature for 2 h.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: and the concentration of the zinc acetate solution in the second step is 0.1 g/mL. Other steps and parameters are the same as those in the first embodiment.
Comparative example: the preparation method of the nitrogen-doped biomass charcoal without adding zinc acetate in the comparative example comprises the following steps:
firstly, taking 30mL of chitosan solution with the concentration of 0.017g/mL, and adjusting the pH value of the chitosan solution to be 12 by using 2mol/L of sodium hydroxide solution;
secondly, uniformly stirring the solution obtained in the first step at the rotation speed of 600rpm, carrying out hydrothermal reaction at 100 ℃ for 8 hours, and then carrying out freeze drying at-80 ℃ for 72 hours;
and thirdly, heating the product obtained in the second step to 700 ℃ at the heating rate of 5 ℃/min under the protection of nitrogen atmosphere, preserving heat for 4h at the temperature, soaking the product in 5% by mass of potassium hydroxide solution for 12h, heating the product to 750 ℃ at the heating rate of 5 ℃/min under the protection of nitrogen atmosphere after soaking, preserving heat for 2h at the temperature, standing the product in 25% by volume of hydrochloric acid for 12h, washing the product with distilled water for 5 times, and finally drying the product at 80 ℃ to obtain the nitrogen-doped biomass charcoal without the zinc acetate of the comparative example.
And (3) detection test:
scanning electron microscope detection is carried out on the zinc oxide auxiliary nitrogen-doped biomass charcoal obtained in the first embodiment, so as to obtain an SEM photo of the zinc oxide auxiliary nitrogen-doped biomass charcoal shown in fig. 1. As can be seen from fig. 1, the zinc oxide with a large pore structure assists the nitrogen-doped biomass char to be distributed relatively uniformly.
And (II) XRD detection is carried out on the zinc oxide auxiliary nitrogen-doped biomass carbon obtained in the first embodiment, the XRD pattern of the zinc oxide auxiliary nitrogen-doped biomass carbon shown in figure 2 is obtained, and as can be seen from figure 2, two diffraction peaks appear at 24 degrees and 43 degrees of 2 theta, which indicates that the zinc oxide auxiliary nitrogen-doped biomass carbon has an amorphous carbon structure.
(III) carrying out XPS spectrum detection on the zinc oxide auxiliary nitrogen-doped biomass charcoal obtained in the first embodiment to obtain an XPS spectrum of the zinc oxide auxiliary nitrogen-doped biomass charcoal as shown in figures 3-6, wherein as can be seen from figures 3-6, the surface of the zinc oxide auxiliary nitrogen-doped biomass charcoal contains C, O, N three elements, wherein O and C exist in the form of single bonds or double bonds, and N has abundant bonding forms on the surface, but takes pyrrole N as a main existence form.
And (IV) performing scanning electron microscope detection on the zinc oxide auxiliary nitrogen-doped biomass charcoal obtained in the second embodiment to obtain an SEM (scanning electron microscope) picture of the zinc oxide auxiliary nitrogen-doped biomass charcoal shown in FIG. 7. As can be seen from fig. 7, the nitrogen-doped biomass charcoal assisted by zinc oxide according to the second embodiment is uniformly distributed and has a porous structure.
And (V) performing antibiotic adsorption experiment effect detection on the zinc oxide auxiliary nitrogen-doped biomass charcoal obtained in the first and second specific embodiments and the nitrogen-doped biomass charcoal without zinc acetate obtained in the comparative example, wherein the specific method comprises the following steps:
0.01g of each of the zinc oxide-assisted nitrogen-doped biomass charcoal obtained in the first embodiment and the zinc acetate-free nitrogen-doped biomass charcoal obtained in the second embodiment and the zinc acetate-free nitrogen-doped biomass charcoal obtained in the comparative example is taken to adsorb 20mL of 50mg/L solutions of three antibiotics (amoxicillin, aureomycin and levofloxacin) at room temperature, so as to obtain a histogram of removal rates of the three antibiotics shown in FIG. 8, as can be seen from FIG. 8, the removal rates of the zinc oxide-assisted nitrogen-doped biomass charcoal obtained in the first embodiment and the second embodiment on the three antibiotics are far higher than that of the zinc acetate-free nitrogen-doped biomass charcoal obtained in the comparative example, and the highest removal rate of the antibiotics in the specific embodiment is nearly 99%.
Claims (10)
1. The preparation method of the zinc oxide-assisted nitrogen-doped biomass charcoal is characterized by comprising the following steps:
firstly, adding chitosan into a glacial acetic acid solution for dissolving to prepare a chitosan solution;
dropwise adding the chitosan solution obtained in the step one into a zinc acetate solution, adjusting the pH value to 9-12 by using a sodium hydroxide solution after the dropwise addition is finished, and uniformly stirring to obtain a mixed solution; the volume ratio of the chitosan solution obtained in the step one to the zinc acetate solution is 3: (1-3);
thirdly, carrying out hydrothermal reaction on the mixed solution obtained in the second step, and then carrying out freeze drying to obtain a chitosan and ZnO combined material;
fourthly, firstly calcining the chitosan and ZnO combination obtained in the third step, then soaking the combination in a potassium hydroxide solution, then carrying out secondary calcining treatment after soaking, then standing the combination in hydrochloric acid, washing the combination with distilled water for 3-5 times after standing, and finally drying the combination at the temperature of 60-100 ℃ to obtain the zinc oxide auxiliary nitrogen-doped biomass carbon.
2. The preparation method of the zinc oxide-assisted nitrogen-doped biomass charcoal as claimed in claim 1, wherein the ratio of the mass of the chitosan to the volume of the glacial acetic acid solution in the first step is (0.01-0.03) g: 1mL, wherein the volume concentration of the glacial acetic acid solution is 1-3%.
3. The preparation method of zinc oxide-assisted nitrogen-doped biomass charcoal as claimed in claim 1, wherein the volume ratio of the chitosan solution and the zinc acetate solution obtained in the first step in the second step is 3: 2; and the concentration of the zinc acetate solution in the second step is 0.03 g/mL-0.15 g/mL.
4. The preparation method of the zinc oxide-assisted nitrogen-doped biomass charcoal as claimed in claim 1, wherein the concentration of the sodium hydroxide solution in the second step is 2mol/L to 5 mol/L.
5. The preparation method of the zinc oxide-assisted nitrogen-doped biomass charcoal according to claim 1, wherein the hydrothermal reaction parameters in step three are as follows: the temperature is 80-150 ℃, and the time is 6-10 h.
6. The preparation method of the nitrogen-doped biomass charcoal assisted by zinc oxide according to claim 1, wherein the freeze-drying parameters in step three are as follows: the temperature is-70 to-90 ℃, and the time is 65 to 80 hours.
7. The preparation method of the nitrogen-doped biomass charcoal assisted by zinc oxide according to claim 1, wherein the primary calcination treatment process in step four specifically comprises: under the protection of nitrogen atmosphere, heating from room temperature to 650-750 ℃ at the heating rate of 3-10 ℃/min, and then preserving heat for 3-5 h at the temperature.
8. The preparation method of nitrogen-doped biomass charcoal assisted by zinc oxide according to claim 1, wherein the mass concentration of the potassium hydroxide solution in the fourth step is 4-6%, and the soaking time is 10-14 h.
9. The preparation method of the nitrogen-doped biomass charcoal assisted by zinc oxide according to claim 1, wherein the secondary calcination treatment process in step four is as follows: under the protection of nitrogen atmosphere, heating from room temperature to 700-800 ℃ at a heating rate of 3-10 ℃/min, and then preserving heat for 1-3 h at the temperature.
10. The preparation method of nitrogen-doped biomass charcoal assisted by zinc oxide according to claim 1, wherein the volume concentration of the hydrochloric acid in the fourth step is 20-30%, and the standing time is 10-14 h.
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| CN109686583A (en) * | 2019-01-22 | 2019-04-26 | 齐鲁工业大学 | A kind of preparation method of porous spongy chitosan-based activated carbon composite material |
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| CN109686583A (en) * | 2019-01-22 | 2019-04-26 | 齐鲁工业大学 | A kind of preparation method of porous spongy chitosan-based activated carbon composite material |
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