CN113041997A - Modified magnetic biochar and preparation method and application thereof - Google Patents
Modified magnetic biochar and preparation method and application thereof Download PDFInfo
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- CN113041997A CN113041997A CN202110244221.3A CN202110244221A CN113041997A CN 113041997 A CN113041997 A CN 113041997A CN 202110244221 A CN202110244221 A CN 202110244221A CN 113041997 A CN113041997 A CN 113041997A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000001035 drying Methods 0.000 claims abstract description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000004140 cleaning Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002028 Biomass Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 240000003537 Ficus benghalensis Species 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000007873 sieving Methods 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 229960000282 metronidazole Drugs 0.000 claims description 15
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 9
- 238000000197 pyrolysis Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 5
- 230000003115 biocidal effect Effects 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000012986 modification Methods 0.000 description 9
- 230000006872 improvement Effects 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
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- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000027756 respiratory electron transport chain Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- -1 sulfate radical Chemical class 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention belongs to the technical field of biochar, and discloses modified magnetic biochar and a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) cleaning banyan branches, drying, crushing and sieving for later use to obtain biomass powder of the banyan branches; 2) adding a nitrogen source and deionized water into biomass powder, stirring, mixing, drying, pyrolyzing the obtained sample under the protection of inert gas, cooling, cleaning, drying, and grinding to obtain nitrogen modified biochar; 3) and (3) taking nitrogen modified biochar, fully mixing with an aqueous solution of metal salt, drying, pyrolyzing the obtained sample under the protection of inert gas, cooling, cleaning, drying, and grinding to obtain the modified magnetic biochar. The modified magnetic biochar has a particularly excellent effect on antibiotic wastewater treatment, and the used modified magnetic biochar can be recycled through an external magnetic field. The preparation process is simple, environment-friendly and economical, meets the requirement of sustainable development, and is easy for industrial production.
Description
Technical Field
The invention belongs to the technical field of biochar, and particularly relates to modified magnetic biochar and a preparation method and application thereof.
Background
Biochar, also called as biomass charcoal, is a porous carbonaceous material produced by thermochemical decomposition of biomass raw materials in a closed environment under low oxygen or anaerobic conditions. The biochar is a porous material rich in carbon, has a structure with high carbon content and aromaticity, a large specific surface area, a rich pore structure and surface active groups, and can effectively remove heavy metals and organic pollutants in water. In addition, the main properties of the biochar are closely related to the raw materials and conditions for preparing the biochar, the biochar derived from different raw materials has different properties, and the biochar derived from the same raw material also has different characteristics due to different preparation conditions. In recent years, more and more researches show that a large number of active groups rich on the surface of the biochar play an important role in promoting electron transfer, catalysis and the like, and efficient degradation of pollutants can be realized by strengthening electron transfer between biological reactions or catalytic oxidation. However, when wastewater is treated by biochar, there are problems that pure biochar has low activity, and the used materials are difficult to recover and regenerate, and particularly, effective control is required for the treatment of antibiotic wastewater.
Disclosure of Invention
The invention provides a modified magnetic biochar and a preparation method and application thereof, which are used for solving one or more technical problems in the prior art and at least providing a beneficial selection or creation condition.
In order to overcome the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of modified magnetic biochar comprises the following steps:
1) cleaning banyan branches, drying, crushing and sieving for later use to obtain biomass powder of the banyan branches;
2) adding a nitrogen source and deionized water into the biomass powder obtained in the step 1), stirring, mixing, drying to obtain a sample A, then pyrolyzing under the protection of inert gas, cooling, cleaning, drying, and grinding to obtain nitrogen modified biochar;
3) and (3) fully mixing the nitrogen modified biochar obtained in the step 2) with an aqueous solution of metal salt, drying to obtain a sample B, then pyrolyzing under the protection of inert gas, cooling, cleaning, drying, and then grinding to obtain the modified magnetic biochar.
As a further improvement of the scheme, in the step 1), the drying temperature is 50-80 ℃, and the drying time is 10-20 h.
As a further improvement of the above scheme, the nitrogen source is at least one selected from melamine, urea or dicyandiamide.
As a further improvement of the above aspect, the metal salt is at least one selected from a nitrate of a metal, a sulfate of a metal, or a chloride of a metal.
As a further improvement of the above scheme, the mass ratio of the nitrate of the metal to the biochar is 10: (1-5). The modified magnetic biochar prepared according to the proportion can effectively avoid the agglomeration phenomenon among metal oxides, accelerate electron transfer and further improve the capacity of removing antibiotics by the modified magnetic biochar.
As a further improvement of the above scheme, the nitrate of the metal is Ce (NO)3)3·6H2O and Fe (NO)3)3·9H2A mixture of O; preferably, the Ce (NO)3)3·6H2O and Fe (NO)3)3·9H2The molar ratio of O is (1-4): 1. the modified magnetic biochar contains more metal oxide species beneficial to activating PMS, and the activation capability of the magnetic biochar is improved.
As a further improvement of the scheme, the pyrolysis temperature is 300-800 ℃, the heating rate is 2-20 ℃/min, and the pyrolysis time is 1-2 h; the stirring time is 1-5 h, and the stirring speed is 200-1000 rpm.
As a further improvement of the above aspect, the inert gas is selected from at least one of nitrogen, argon, and helium; the flow rate of the inert gas is 50-300 mL/min.
The modified magnetic biochar is prepared by the preparation method provided by the invention, and the removal rate of metronidazole by the modified magnetic biochar is greater than 90% within 30 min.
The modified magnetic biochar prepared by the preparation method disclosed by the invention is applied to wastewater treatment, and is particularly suitable for treating antibiotic wastewater.
The invention has the beneficial effects that:
the modified magnetic biochar has a particularly excellent effect on antibiotic wastewater treatment, and in the case of metronidazole, the modified magnetic biochar is added into a solution containing metronidazole, and the metronidazole is rapidly degraded and removed through oxidation, so that the used modified magnetic biochar can be recycled through an external magnetic field. Therefore, compared with the prior art, the raw materials for preparing the biochar are convenient and easy to obtain and have wide sources, and the process of preparing the biochar realizes waste recycling; compared with unmodified biochar, the modified magnetic biochar has obviously improved capacity of removing antibiotics and is easy to recycle; in addition, the preparation process is simple, environment-friendly and economical, meets the requirement of sustainable development, and is easy for industrial production.
Drawings
FIG. 1 shows CeFe obtained in example 12O5N-BC and CeFe obtained in comparative example 12O5A performance comparison graph of the/BC on the metronidazole wastewater purification efficiency respectively;
FIG. 2 is a graph showing the magnetic properties of biochar before and after loading with metal oxide;
FIG. 3 is a comparison of the morphology of biochar before and after modification.
Detailed Description
The present invention is specifically described below with reference to examples in order to facilitate understanding of the present invention by those skilled in the art. It should be particularly noted that the examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as non-essential improvements and modifications to the invention may occur to those skilled in the art, which fall within the scope of the invention as defined by the appended claims. Meanwhile, the raw materials mentioned below are not specified in detail and are all commercially available products; the process steps or extraction methods not mentioned in detail are all process steps or extraction methods known to the person skilled in the art.
Example 1
A preparation method of modified magnetic biochar comprises the following steps:
1) cleaning banyan branches, drying in a 70 ℃ oven for 24h, crushing by a crusher, and sieving to obtain biomass powder of 10-mesh banyan branches;
2) mixing biomass powder and urea in a deionized water solution according to a mass ratio of 1:4, stirring for 2h, mixing, drying in a 70 ℃ oven, putting the obtained sample in a tubular furnace, heating to 500 ℃ at a speed of 10 ℃/min under the atmosphere of 100mL/min of nitrogen, pyrolyzing at a constant temperature for 2h, cooling to room temperature, cleaning, drying, grinding, washing with absolute ethyl alcohol and deionized water, drying, and sieving with a 50-mesh sieve to obtain nitrogen modified biochar which is marked as biochar N-BC;
3) taking the nitrogen modified biochar obtained in the step 2), and mixing the nitrogen modified biochar with 2.5mmol of Ce (NO) according to the mass ratio of 1:43)3·6H2O and 2.5mmol of Fe (NO)3)3·9H2Mixing O in the water solution, stirring for 2h, drying in an oven at 70 ℃, putting in a tube furnace, heating to 500 ℃ at the speed of 10 ℃/min under the atmosphere of nitrogen gas 100mL/min, and pyrolyzing at constant temperature for 2 h. Cooling to room temperature, grinding, washing with anhydrous ethanol and deionized water, drying, and sieving with 50 mesh sieve to obtain magnetic charcoal CeFe2O5/N-BC。
Comparative example 1
Comparative example 1 differs from example 1 in that comparative example 1 has no urea added. The preparation method comprises the following whole processes:
1) cleaning banyan branches, drying in a 70 ℃ oven for 24h, crushing by a crusher, and sieving to obtain biomass powder of 10-mesh banyan branches;
2) mixing biomass powder in a deionized water solution, stirring for 2h, mixing, drying in a 70 ℃ oven, putting the obtained sample in a tubular furnace, heating to 500 ℃ at the speed of 10 ℃/min under the atmosphere of 100mL/min of nitrogen, pyrolyzing at constant temperature for 2h, cooling to room temperature, cleaning, drying, grinding, washing with absolute ethyl alcohol and deionized water, drying, and sieving with a 50-mesh sieve to obtain unmodified biochar BC;
3) mixing charcoal powder with 2.5mmol of Ce (NO) at a mass ratio of 1:43)3·6H2O and 2.5mmol of Fe (NO)3)3·9H2Mixing O in the water solution, stirring for 2h, drying at 70 ℃ in an oven, placing in a tube furnace, heating to 500 ℃ at the speed of 10 ℃/min under the atmosphere of nitrogen gas 100mL/min, pyrolyzing at constant temperature for 2h, cooling to room temperature, grinding, washing with absolute ethyl alcohol and deionized water, drying, and sieving with a 50-mesh sieve to obtain the magnetic biochar CeFe2O5/BC。
Product Performance test 1
Biochar BC and biochar N-BC, CeFe obtained in example 1 and comparative example 12O5BC and CeFe2O5the/N-BC was dosed to metronidazole wastewater containing 10mg/g at 0.5g/L, and under the conditions of PMS (Peroxymonosulfonate), named as peroxymonosulfate) concentration of 1mM, and reaction temperature of 25 deg.C, FIG. 1 (FIG. 1 is CeFe obtained in example 1)2O5N-BC and CeFe obtained in comparative example 12O5The performance comparison graph of the/BC on the purification efficiency of the metronidazole wastewater respectively, and the ordinate of the performance comparison graph is the removal rate of the metronidazole), as can be seen from the graph 1, before the catalyst is not added, the degradation rate of the single PMS on the metronidazole is 33%, and after the magnetic biochar composite material is added, the removal rate of the metronidazole is obviously improved and reaches 55% within 30 minutes. Furthermore, after nitrogen modification of the composite, CeFe2O5The removal rate of metronidazole by the/N-BC + PMS system is up to 83.7%. Therefore, the magnetic biochar composite material has the advantage of being better for PMSGood activation capability and is beneficial to the degradation of metronidazole after N is doped. Thus, fig. 1 effectively illustrates that the incorporation of N is beneficial to improve the metronidazole degradation performance of the bimetal-loaded magnetic biochar. At the same time, it can be clearly seen that the biological carbon CeFe2O5The removal rate of metronidazole by the/N-BC in 30min is more than 90%, and the effect is optimal.
This is mainly due to the fact that, under pyrolysis conditions at high temperatures, Ce (NO)3)3·6H2O and Fe (NO)3)3·9H2Oxide CeFe obtained after O pyrolysis2O5Can effectively activate PMS to generate active groups with strong oxidizing ability, and meanwhile, the doping of the N source can generate active N species which are beneficial to PMS activation, such as pyridine nitrogen, graphite nitrogen and the like. The doped non-metal N occupies the active site of the carbon-based material, replaces the original oxygen, and leads the electrons of the composite material to be gathered to the N, thereby leading the N to become the active site of the composite material. When the active site meets asymmetric PMS, electron transfer can occur, a large amount of singlet oxygen, hydroxyl free radicals, sulfate free radicals and other active oxygen species are generated, and pollutants in water are further degraded. The graphitized nitrogen added by N doping can activate PMS to generate singlet oxygen through a non-free radical way to improve the degradation effect, and the pyridine nitrogen can activate PMS to generate hydroxyl free radicals and sulfate free radicals through an enhanced free radical way to improve the reaction rate.
At the same time, by adding Ce (NO)3)3·6H2O, can promote Fe3+/Fe2+And Ce4+/Ce3+The circulation of redox electron pair enables the oxidation reaction of PMS to generate an effective electron transfer process, and accelerates sulfate radical (SO)4 -Can effectively improve the degradation efficiency of the organic matters.
Product Performance test 2
The biochar CeFe obtained in the example 1 and subjected to bimetal modification2O5N-BC, compared with the non-magnetized biochar N-BC obtained in the comparative example 1, the biochar before loading the bimetallic oxide is taken as shown in figure 2, the right beaker is the biochar before loading the bimetallic oxide,the beaker on the left is the biochar loaded with the bimetallic oxide, and after the biochar is stirred for 30min by a magnetic stirrer, the biochar material is still uniformly dispersed in the solution, which shows that the biochar not loaded with the bimetallic oxide can not be attracted by a magnetic stirrer, namely is not magnetic. Compared with the biochar which is not loaded with the bimetallic oxide, under the same condition, after being stirred by a magnetic stirrer, most of the biochar is attracted by a magnetic stirrer, and the solution is in a clear state, namely the loaded biochar is magnetic. Therefore, the magnetism of the biochar loaded by the bimetal is obviously enhanced.
Fig. 3 is a Scanning Electron Microscope (SEM) before and after the modification of the biochar, wherein a is a SEM before the modification of the biochar, and b is a SEM after the modification of the biochar. As shown in a of fig. 3, the pure biochar before modification has a large structure and a relatively smooth surface. In contrast, modified CeFe2O5The morphology of the/N-BC changed significantly (as shown in b of FIG. 3). CeFe2O5the/N-BC exhibits a very pronounced lamellar and wrinkled morphology, probably due to the formation of abundant defects due to the incorporation of nitrogen atoms into the graphitic carbon network, which may be one of the reasons for better catalytic performance of the material. In addition, irregular bulges appear on the surface of the modified material, which is probably caused by the attachment of metal oxides formed in the pyrolysis process on the surface of the biochar.
It will be obvious to those skilled in the art that many simple derivations or substitutions can be made without inventive effort without departing from the inventive concept. Therefore, simple modifications to the present invention by those skilled in the art according to the present disclosure should be within the scope of the present invention. The above embodiments are preferred embodiments of the present invention, and all similar processes and equivalent variations to those of the present invention should fall within the scope of the present invention.
Claims (10)
1. The preparation method of the modified magnetic biochar is characterized by comprising the following steps:
1) cleaning banyan branches, drying, crushing and sieving for later use to obtain biomass powder of the banyan branches;
2) adding a nitrogen source and deionized water into the biomass powder obtained in the step 1), stirring, mixing, drying to obtain a sample A, then pyrolyzing under the protection of inert gas, cooling, cleaning, drying, and grinding to obtain nitrogen modified biochar;
3) and (3) fully mixing the nitrogen modified biochar obtained in the step 2) with an aqueous solution of metal salt, drying to obtain a sample B, then pyrolyzing under the protection of inert gas, cooling, cleaning, drying, and then grinding to obtain the modified magnetic biochar.
2. The preparation method of claim 1, wherein in the step 1), the drying temperature is 50-80 ℃, and the drying time is 10-20 h.
3. The method according to claim 1, wherein the nitrogen source is at least one selected from melamine, urea, and dicyandiamide.
4. The production method according to claim 1, wherein the metal salt is at least one selected from a nitrate of a metal, a sulfate of a metal, and a chloride of a metal.
5. The preparation method according to claim 1, wherein the mass ratio of the metal salt to the nitrogen-modified biochar is 10: (1-5).
6. The method according to claim 4, wherein the nitrate of the metal is Ce (NO)3)3And Fe (NO)3)3A mixture of (a); preferably, the Ce (NO)3)3And Fe (NO)3)3The molar ratio of (1-4): 1.
7. the preparation method according to claim 1, wherein the pyrolysis temperature is 300-800 ℃, the heating rate is 2-20 ℃/min, and the pyrolysis time is 1-2 h; the stirring time is 1-5 h, and the stirring speed is 200-1000 rpm.
8. The production method according to claim 1, wherein the inert gas is selected from at least one of nitrogen, argon, and helium; the flow rate of the inert gas is 50-300 mL/min.
9. The modified magnetic biochar is prepared by the preparation method of any one of claims 1 to 8, and the removal rate of metronidazole within 30min is greater than 90%.
10. Use of the modified magnetic biochar of claim 9 in wastewater treatment.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114433022A (en) * | 2022-01-18 | 2022-05-06 | 北京工商大学 | Metal modified activated carbon adsorbent derived from sugarcane peel, preparation method and application thereof |
| CN114515577A (en) * | 2021-12-31 | 2022-05-20 | 长沙学院 | Cerium-doped magnetic biochar and preparation method and application thereof |
| CN115738998A (en) * | 2022-11-25 | 2023-03-07 | 师大(清远)环境修复科技有限公司 | Nitrogen-doped magnetic biochar as well as preparation method and application thereof |
| CN115738997A (en) * | 2022-11-23 | 2023-03-07 | 东北农业大学 | Preparation method and application of cerium-iron co-modified hydrophilic porous biochar |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628211A (en) * | 2015-02-11 | 2015-05-20 | 四川大学 | Method for removing endocrine disrupters in water by activating persulfate under synergic catalytic actions of metal cerium and magnetic reduced graphene oxide |
| US20150295248A1 (en) * | 2011-06-15 | 2015-10-15 | Stc.Unm | Cathode catalysts for fuel cell application derived from polymer precursors |
| CN106565647A (en) * | 2016-10-29 | 2017-04-19 | 华东理工大学 | Method for preparing 2, 5-furandicarboxylic acid by conducting catalytic oxidation on 5-hydroxymethylfurfural |
| WO2018099173A1 (en) * | 2016-12-02 | 2018-06-07 | 建添企业有限公司 | Method for preparing nitrogen-doped porous carbon material by using coal as raw material |
| CN108993510A (en) * | 2018-08-16 | 2018-12-14 | 南京工业大学 | A kind of activation persulfate tire C catalyst and preparation and application |
| CN109499529A (en) * | 2018-11-01 | 2019-03-22 | 华东理工大学 | A kind of magnetic porous carbon material of N doping and its preparation method and application |
| CN109589979A (en) * | 2017-09-30 | 2019-04-09 | 黑龙江大学 | A kind of metal oxide/carbon material compound and its preparation method and application |
| CN109769806A (en) * | 2018-11-14 | 2019-05-21 | 浙江农林大学 | A kind of sustained release algae removal microcapsules and preparation method thereof |
| CN110252242A (en) * | 2019-05-17 | 2019-09-20 | 兰州大学 | A kind of preparation method and modification biological charcoal of modification biological charcoal |
| CN111001415A (en) * | 2019-12-25 | 2020-04-14 | 佛山科学技术学院 | Preparation method of composite oxide low-temperature denitration catalyst and catalyst |
| CN111821982A (en) * | 2020-04-26 | 2020-10-27 | 闽南师范大学 | Graphene oxide-cerium oxide-iron oxide composite material, synthesis method and application of graphene oxide-cerium oxide-iron oxide composite material in catalytic degradability |
-
2021
- 2021-03-05 CN CN202110244221.3A patent/CN113041997A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150295248A1 (en) * | 2011-06-15 | 2015-10-15 | Stc.Unm | Cathode catalysts for fuel cell application derived from polymer precursors |
| CN104628211A (en) * | 2015-02-11 | 2015-05-20 | 四川大学 | Method for removing endocrine disrupters in water by activating persulfate under synergic catalytic actions of metal cerium and magnetic reduced graphene oxide |
| CN106565647A (en) * | 2016-10-29 | 2017-04-19 | 华东理工大学 | Method for preparing 2, 5-furandicarboxylic acid by conducting catalytic oxidation on 5-hydroxymethylfurfural |
| WO2018099173A1 (en) * | 2016-12-02 | 2018-06-07 | 建添企业有限公司 | Method for preparing nitrogen-doped porous carbon material by using coal as raw material |
| CN109589979A (en) * | 2017-09-30 | 2019-04-09 | 黑龙江大学 | A kind of metal oxide/carbon material compound and its preparation method and application |
| CN108993510A (en) * | 2018-08-16 | 2018-12-14 | 南京工业大学 | A kind of activation persulfate tire C catalyst and preparation and application |
| CN109499529A (en) * | 2018-11-01 | 2019-03-22 | 华东理工大学 | A kind of magnetic porous carbon material of N doping and its preparation method and application |
| CN109769806A (en) * | 2018-11-14 | 2019-05-21 | 浙江农林大学 | A kind of sustained release algae removal microcapsules and preparation method thereof |
| CN110252242A (en) * | 2019-05-17 | 2019-09-20 | 兰州大学 | A kind of preparation method and modification biological charcoal of modification biological charcoal |
| CN111001415A (en) * | 2019-12-25 | 2020-04-14 | 佛山科学技术学院 | Preparation method of composite oxide low-temperature denitration catalyst and catalyst |
| CN111821982A (en) * | 2020-04-26 | 2020-10-27 | 闽南师范大学 | Graphene oxide-cerium oxide-iron oxide composite material, synthesis method and application of graphene oxide-cerium oxide-iron oxide composite material in catalytic degradability |
Non-Patent Citations (2)
| Title |
|---|
| CHENG-DI DONG ET AL.,: ""Degradation of phthalate esters in marine sediments by persulfate over Fe–Ce/biochar composites"" * |
| LU XU ET AL.,: ""Peroxymonosulfate activation by nitrogen-doped biochar from sawdust for the efficient degradation of organic pollutants"" * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114515577A (en) * | 2021-12-31 | 2022-05-20 | 长沙学院 | Cerium-doped magnetic biochar and preparation method and application thereof |
| CN114515577B (en) * | 2021-12-31 | 2023-11-03 | 长沙学院 | Cerium doped magnetic biochar and preparation method and application thereof |
| CN114433022A (en) * | 2022-01-18 | 2022-05-06 | 北京工商大学 | Metal modified activated carbon adsorbent derived from sugarcane peel, preparation method and application thereof |
| CN114433022B (en) * | 2022-01-18 | 2023-11-03 | 北京工商大学 | Metal modified activated carbon adsorbent derived from sugarcane skin, preparation method and application thereof |
| CN115738997A (en) * | 2022-11-23 | 2023-03-07 | 东北农业大学 | Preparation method and application of cerium-iron co-modified hydrophilic porous biochar |
| CN115738998A (en) * | 2022-11-25 | 2023-03-07 | 师大(清远)环境修复科技有限公司 | Nitrogen-doped magnetic biochar as well as preparation method and application thereof |
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