CN117384647B - Furillic acid composite nitrogen-doped magnetic carbon submicron sphere and preparation method and application thereof - Google Patents
Furillic acid composite nitrogen-doped magnetic carbon submicron sphere and preparation method and application thereof Download PDFInfo
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- CN117384647B CN117384647B CN202311684740.7A CN202311684740A CN117384647B CN 117384647 B CN117384647 B CN 117384647B CN 202311684740 A CN202311684740 A CN 202311684740A CN 117384647 B CN117384647 B CN 117384647B
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- fulvic acid
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 130
- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002253 acid Substances 0.000 title description 8
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 claims abstract description 98
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 claims abstract description 98
- 239000002509 fulvic acid Substances 0.000 claims abstract description 98
- 229940095100 fulvic acid Drugs 0.000 claims abstract description 98
- 239000002689 soil Substances 0.000 claims abstract description 76
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 69
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 59
- 229940088710 antibiotic agent Drugs 0.000 claims abstract description 59
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims abstract description 11
- 230000003115 biocidal effect Effects 0.000 claims abstract description 10
- 229960003638 dopamine Drugs 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 9
- 125000000524 functional group Chemical group 0.000 claims abstract description 7
- 238000005067 remediation Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000003763 carbonization Methods 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 17
- 239000012265 solid product Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007833 carbon precursor Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000010000 carbonizing Methods 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 239000004005 microsphere Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002905 metal composite material Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
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- 229910003471 inorganic composite material Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 24
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 238000005406 washing Methods 0.000 description 9
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 7
- 239000004098 Tetracycline Substances 0.000 description 6
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
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- 241000196324 Embryophyta Species 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 229960003405 ciprofloxacin Drugs 0.000 description 4
- 230000036541 health Effects 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
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- 241000282414 Homo sapiens Species 0.000 description 3
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- 238000011068 loading method Methods 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 2
- 206010059866 Drug resistance Diseases 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- -1 amino, hydroxyl Chemical group 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 229940124307 fluoroquinolone Drugs 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000001477 organic nitrogen group Chemical group 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 description 1
- 241000196133 Dryopteris Species 0.000 description 1
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000010802 Oxidation-Reduction Activity Effects 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 244000299790 Rheum rhabarbarum Species 0.000 description 1
- 235000009411 Rheum rhabarbarum Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000000685 anti-plasmid Effects 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
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- 239000011425 bamboo Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 229960001149 dopamine hydrochloride Drugs 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
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- 244000144972 livestock Species 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
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- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 244000000010 microbial pathogen Species 0.000 description 1
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- 239000002808 molecular sieve Substances 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- 239000002957 persistent organic pollutant Substances 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
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Classifications
-
- 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
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2101/00—Agricultural use
Abstract
The invention discloses a fulvic acid composite nitrogen-doped magnetic carbon submicron sphere and a preparation method and application thereof, belonging to the technical field of carbon material preparation and soil remediation application. The invention synthesizes dopamine, iron (III) acetate and fulvic acid through a chemical liquid phase deposition method to prepare the fulvic acid composite nitrogen-doped magnetic carbon submicron sphere, and the surface of the material contains a large amount of-NH 2 The organic-inorganic composite material has the advantages of multiple active functional groups such as-OH, more adsorption sites, large specific surface area, strong magnetism, environmental protection, good adsorption and removal effects on various antibiotics, heavy metals and antibiotic heavy metal complexes, and simultaneously provides carbon sources and nitrogen sources for the activities of soil microorganisms, increases the activities of microorganisms, improves the materialized composition and structure of the soil, promotes the growth of plants, and finally achieves the purposes of soil remediation, ecological restoration and environmental greening.
Description
Technical Field
The invention relates to the technical field of carbon material preparation and soil remediation application, in particular to a fulvic acid composite nitrogen-doped magnetic carbon submicron sphere and a preparation method and application thereof.
Background
With the rapid development of the pharmaceutical industry, a large number of antibiotics are beginning to be used as medicines and are rapidly being widely used throughout the world. At present, the antibiotics are widely applied, and relate to various fields of production and life, including medical and health, agricultural production, livestock and poultry cultivation, aquaculture and the like. Antibiotics are effective against or inhibit pathogenic microorganisms in higher animals and are of a wide variety of types including Tetracyclines (TCs), fluoroquinolones (FQs), sulfonamides (sass), and the like. However, only a small part of antibiotics can be absorbed by organisms and act, and most of antibiotics are difficult to be absorbed by the organisms in a metabolizing way, so that prototype or metabolic products thereof can be directly discharged out of the body along with the biological excrement and urine. The waste or wastewater containing antibiotics can induce microorganisms to generate drug resistance after not being effectively treated into an environmental medium, and drug-resistant bacteria and resistance genes are formed, so that the balance of an ecological system is finally destroyed, and potential threats are formed for human health and ecological environment safety.
The contaminants are not present in the environmental system alone, often in the environmental medium by the co-presence of multiple contaminants. With the rapid development of industry, metal manufacturing industry, electroplating industry, mineral collection, leather making factory, electronic industry and the like are rapidly industrialized, and more heavy metals enter the environment in a direct or indirect way, so that the global environmental problem is caused. Besides industrial activity emissions, heavy metals are often added as growth-promoting trace elements to pesticides, fertilizers and animal feeds, which are also one of the causes of heavy metal pollution. Heavy metals have toxicity, are long in retention time in nature, are difficult to degrade naturally, belong to persistent pollutants, can be continuously accumulated in a ecological system, and finally threaten the health and even the life of animals, plants and human beings.
The antibiotic pollution and the heavy metal pollution are very serious environmental problems, the existence of the antibiotic and the heavy metal can be detected in water and soil in a plurality of areas in China, and the situation that the two pollutants coexist in a compound way in the actual environment is common. Studies have shown that antibiotic-heavy metal complexes alter the physicochemical properties of the antibiotic itself. The combination of the electron donor-containing group of the antibiotic with the heavy metal cation allows the charge of the antibiotic itself to be neutralized, thus becoming more stable, and the persistence of the antibiotic in the environment may thus be enhanced. The composite coexistence of antibiotics and heavy metals can also influence the antibacterial activity, bioavailability, degradation and the like of the antibiotics. It has the same or stronger antibacterial effect as the complex of heavy metals compared to the free antibiotic. Antibiotics and heavy metals can also maintain anti-plasmid at very low concentration levels, and resistance genes are positively correlated with heavy metal content. The long-term exposure to the combined pollution of antibiotics and heavy metals can lead to the generation and transmission of drug resistance genes, even the evolution of multiple resistance genes, and destroy ecological environment, thereby endangering the health of human beings. How to achieve removal of complex contaminants in the presence of antibiotics and heavy metals becomes a difficulty in hot spots.
At present, various methods for removing antibiotics and heavy metals in soil exist, such as chemical precipitation, ion exchange, advanced oxidation, electrochemical methods, biological treatment methods and the like. However, the disadvantages of high running cost, long period, and susceptibility to secondary pollution limit their large-scale application.
Disclosure of Invention
In order to solve the technical problems, the invention provides a fulvic acid composite nitrogen-doped magnetic carbon submicron sphere and a preparation method and application thereof. The fulvic acid composite nitrogen-doped magnetic carbon submicron spheres prepared by the method can supplement soil nutrients and promote the recovery and stability of a soil structure; on the other hand, the method can improve the current situation of the combined pollution of soil antibiotics and heavy metals, can be recycled, and avoids secondary pollution to the soil while recycling.
The first aim of the invention is to provide a preparation method of fulvic acid composite nitrogen-doped magnetic carbon submicron spheres, which comprises the following steps:
s1, mixing and reacting an ethanol water solution containing ammonia water with a dopamine solution to obtain a nitrogen-doped carbon precursor, and heating and carbonizing the nitrogen-doped carbon precursor in an inert atmosphere to obtain nitrogen-doped carbon submicron spheres;
s2, mixing the nitrogen-doped carbon submicron spheres with an alkaline substance, carbonizing in an inert atmosphere, and performing solid-liquid separation to obtain a solid phase, wherein the obtained solid phase is porous nitrogen-doped carbon submicron spheres;
s3, mixing and stirring the dispersion liquid of the porous nitrogen-doped carbon submicron spheres with iron (III) acetate, performing solid-liquid separation to obtain a solid product, and carbonizing the obtained solid product in an inert atmosphere to obtain the nitrogen-doped magnetic carbon submicron spheres;
and S4, mixing and stirring the fulvic acid solution and the dispersion liquid of the nitrogen-doped magnetic carbon submicron spheres for reaction, and drying the solid matters obtained by the reaction to obtain the fulvic acid composite nitrogen-doped magnetic carbon submicron spheres.
In one embodiment of the invention, in step S1, at least one or more of the following conditions are satisfied:
the volume ratio of ammonia water, ethanol and water in the aqueous ethanol solution containing ammonia water is (0.5-2.0): (25-80): (80-150); the concentration of the ammonia water is 28-30wt%;
the concentration of the dopamine solution is 3-6wt%;
the mixing time is 18-36 h;
in the heating carbonization, the heating rate is 3-10 ℃/min, the carbonization temperature is 700-800 ℃, and the carbonization time is 1-2 h;
the inert atmosphere is inert gas such as argon and/or nitrogen.
The method further comprises the step of cleaning the nitrogen-doped carbon precursor for 3-5 times by using ethanol and deionized water as cleaning solutions.
In one embodiment of the invention, in step S2, at least one or more of the following conditions are satisfied:
the mass ratio of the nitrogen-doped carbon submicron spheres to the alkaline substance is (1-3): (2-10);
the alkaline substance is selected from potassium hydroxide and/or sodium hydroxide;
the carbonization process comprises the following steps: heating to the low-temperature carbonization temperature of 400-500 ℃ at a heating rate of 5-10 ℃/min, and the carbonization time of 1-2 h; then heating to a high-temperature carbonization temperature of 700-800 ℃ for 1-2 h;
the inert atmosphere is inert gas such as argon and/or nitrogen.
In one embodiment of the invention, in step S3, at least one or more of the following conditions are satisfied:
the solvent of the dispersion liquid of the porous nitrogen-doped carbon submicron spheres is water;
the mass ratio of the porous nitrogen-doped carbon submicron sphere to the iron (III) acetate is (0.1-0.5): (0.1 to 0.35);
the mixing and stirring time is 12-24 hours, and the solid product obtained by centrifuging the stirred mixed solution is washed for 3-5 times by ethanol and deionized water and dried;
the temperature rising rate in carbonization is 5-10 ℃/min, the carbonization temperature is 700-800 ℃, and the carbonization time is 1-2 h;
the method further comprises the steps of cleaning the obtained nitrogen-doped magnetic carbon submicron spheres, wherein a cleaning agent is an acid solution, mixing and stirring for 6-12 hours at room temperature, washing with water for 3-5 times, and drying.
Further, the acid in the acid solution is a conventional acid in the art, and is not particularly limited, and is selected from sulfuric acid, hydrochloric acid, and the like;
further, the concentration of the acid solution is 0.1-1 mol/L.
In one embodiment of the invention, in step S4, at least one or more of the following conditions are satisfied:
the concentration of the fulvic acid solution is 1 mg/L-10 mg/L;
the pH value of the fulvic acid solution is 7-8;
the solvent of the fulvic acid solution is sodium hydroxide solution with the concentration of 0.05mol/L to 0.2 mol/L;
the method also comprises the step of repeatedly filtering the fulvic acid solution for 3-5 times through a 0.45 mu m filter membrane;
the volume ratio of the mass of the nitrogen-doped magnetic carbon submicron spheres to the fulvic acid solution is (0.1-0.5): (20-30) (g/mL);
the mixing and stirring time is 12-24 hours;
and centrifuging the reaction liquid after the mixed stirring reaction, washing a solid product obtained by centrifugation with ethanol and deionized water for 3-5 times, and drying to obtain the fulvic acid composite nitrogen-doped magnetic carbon submicron spheres.
The second object of the invention is to provide the fulvic acid composite nitrogen-doped magnetic carbon submicron sphere obtained by the preparation method, wherein the fulvic acid composite nitrogen-doped magnetic carbon submicron sphere comprises magnetic nitrogen-doped carbon submicron spheres and the fulvic acid and zero-valent iron/maghemite compound loaded on the surface of the magnetic nitrogen-doped carbon submicron sphere.
In one embodiment of the invention, the fulvic acid composite nitrogen-doped magnetic carbon sub-microsphere satisfies one or more of the following properties:
the particle size of the fulvic acid composite nitrogen-doped magnetic carbon submicron sphere is 100 nm-900 nm;
the magnetic strength is more than or equal to 25emg/g;
the surface is rich in a plurality of active functional groups.
Further, the reactive functional group is-NH 2 、-OH;
The third purpose of the invention is to provide the application of the fulvic acid composite nitrogen-doped magnetic carbon submicron spheres in repairing the composite pollution of soil antibiotics and heavy metals.
In one embodiment of the invention, the adding mass of the fulvic acid composite nitrogen-doped magnetic carbon submicron spheres is 4% -8% of the mass of the soil polluted by the antibiotics and heavy metals.
In one embodiment of the invention, in the soil restoration process, the curing time after mixing and stirring of the fulvic acid composite nitrogen-doped magnetic carbon submicron spheres and the composite polluted soil is more than or equal to 14d, and the soil restoration depth is 0-5 m.
In one embodiment of the invention, in the soil remediation process, the soil polluted by antibiotics and heavy metals to be remediated is pretreated, the fulvic acid composite nitrogen-doped magnetic carbon submicron spheres are added into the pretreated soil, and after the addition, a turning machine is adopted to uniformly mix and solidify.
Further preferably, the soil subjected to the combined pollution of the antibiotics and the heavy metals is not particularly limited, and for better soil restoration effect, the soil subjected to the pretreatment generally has a particle size of less than or equal to 6nm, a pH value of 5-10, an electrical conductivity of 90-400 mu s/cm and a water content of 40-60%; the grain diameter of the soil after the stirring and throwing mechanical mixing is less than or equal to 2nm.
Further, the antibiotics are conventional in the art, and may include antibiotics such as tetracyclines, ciprofloxacin, sulfonamides, and the like, without particular limitation.
Further, the heavy metal is a heavy metal conventional in the art, and may be one or more of Cu, hg, cd, pb, zn, as, cr, ni without particular limitation.
Compared with the prior art, the technical scheme of the invention has the following advantages:
the preparation method of the fulvic acid composite nitrogen-doped magnetic carbon submicron spheres is simple, green and environment-friendly and has low cost. According to the invention, traditional synthesis raw materials (biomass carbon, graphene, polysaccharide polymer, carbon nano tube and the like) are abandoned, nontoxic and widely existing dopamine (PDA) is used as a nitrogen source and a carbon source of a nitrogen-doped carbon precursor, and the nitrogen-doped porous magnetic carbon submicron sphere is prepared. The invention can be directly polymerized into monodisperse submicron spheres without using any template (such as mesoporous silicon molecular sieve, spherical SiO) 2 Particles, tetraethoxysilane, hexadecyl trimethyl ammonium chloride, carbonate, noble metal and the like), and has the advantages of convenient operation of the synthesis process, no need of complex instruments, mild experimental conditions (room temperature) and the like. In addition, compared with traditional carbon materials such as phenol/formaldehyde, the dopamine is a catechol natural substance, has rich functional groups, provides additional active sites for combination with metal ions, organic molecules, functional polymers and the like, makes the catechol/formaldehyde multifunctional platform for secondary surface functionalization, has strong chelating ability on the metal ions due to catechol, amino, hydroxyl and the like, and has wide application prospect in the field of treating heavy metal pollution. The dopamine also has a certain oxidation-reduction activity, and the structure of the coexistence of the phenol and the quinone is an effective oxidation-reduction medium which can promote electron transfer and has remarkable effect on degrading antibiotic organic pollutants.
In the invention, the carbon spheres loaded by the fulvic acid successfully obtain active sites in oxides of different nitrogen configurations, hybridized carbon and iron (hydroxy), and have rich N-H, C (identical to N, C) -O, C-N, C-Fe, fe-O and other bonds. Heavy metal ions and antibiotics in a movable form can be adsorbed on the surface of the material through electrostatic action, hydrogen bonding action, surface coprecipitation and pi-pi bonding action, so that the adsorption-desorption balance between original soil and water is broken, the balance is continuously pushed to the adsorption material end, and the migration and removal of the heavy metals and the antibiotics are completed.
Compared with the adsorbent prepared from the traditional carbon material, the fulvic acid composite nitrogen-doped magnetic carbon submicron sphere prepared by the invention has extremely large surface area (more than or equal to 2000 m) by taking the biological molecule dopamine as the carbon-based material and adopting the chemical liquid phase deposition method to synthesize the fulvic acid and the iron (III) acetate 2 /g) and larger pore volumes (. Gtoreq.1.95 cm) 3 Per gram), the grain diameter is in the submicron range of 100 nm-900 nm, the magnetic strength is more than or equal to 25emg/g, and the surface is rich in-NH 2 Various active functional groups such as-OH, and the like, has the advantages of low toxicity, excellent thermal stability, high dispersibility and the like, the adsorption and degradation effects on antibiotics (80.13% -97.25%) and heavy metals (83.72% -91.35%) in soil are excellent. The prepared fulvic acid composite nitrogen-doped magnetic carbon submicron spheres can obviously improve the characteristics of poor repairing effect, high repairing cost and easiness in damaging soil structures of the traditional soil repairing materials, have a large number of irregular bulges and holes on the surface, and contain rich functional groups on the surface, so that the fulvic acid composite nitrogen-doped magnetic carbon submicron spheres can efficiently adsorb and degrade antibiotics and heavy metals in soil.
And fourthly, the fulvic acid composite nitrogen-doped magnetic carbon submicron spheres prepared by the invention can also play a role of slow release fertilizer. The raw materials dopamine and fulvic acid for preparing the fulvic acid composite nitrogen-doped magnetic carbon submicron spheres can provide carbon sources and nitrogen sources for microbial communities in soil, so that the microbial activity is increased, and the materialized composition and structure of the soil are improved. Microorganisms in the soil can convert organic nitrogen into inorganic nitrogen, so that the organic nitrogen is absorbed by plant roots to promote plant growth, and finally the purposes of soil restoration, ecological restoration and environmental greening are achieved. Meanwhile, when the curing reaction time is more than or equal to 14d, the carbon submicron spheres basically complete the degradation of antibiotics and the adsorption of heavy metals, and form a large number of scattered micro habitats in soil, wherein the habitats are rich in carbon sources, nitrogen sources, microorganisms, adsorbed heavy metals and the like. If heavy metal is in the light pollution area, extraction is not needed; for example, in heavy metal contaminated areas, super-enriched plants such as bamboo shoot grass, rhubarb, bitter grass, dryopteris crassifolia and the like can be planted in the soil, the super-enriched plants have the characteristic of super-enriching heavy metal elements, and the accumulated metal elements can be used in the fields of pharmacy, metallurgy and the like.
And fifthly, the fulvic acid composite nitrogen-doped magnetic carbon submicron spheres are subjected to chemical modification by alkali, so that the pore volume, the pore diameter and the specific surface area of the carbon spheres can be improved, the organic iron ion compound iron (III) acetate and the fulvic acid are favorably loaded by a chemical liquid phase deposition method, the structural properties of the loaded carbon spheres are obviously changed, the surfaces are coarsened and porous, and the magnetic carbon submicron spheres have high magnetization intensity and good stability due to the addition of iron, so that the magnetic carbon submicron spheres have magnetic separation potential and can be recycled by means of an externally applied magnetic field and the like.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which,
fig. 1 is an SEM image of the fulvic acid composite nitrogen-doped magnetic carbon sub-micron spheres obtained in example 2 of the present invention.
FIG. 2 is a graph showing the comparison of adsorption rates of typical antibiotics and heavy metals in soil after 0 to 5 times of regeneration of the fulvic acid composite nitrogen-doped carbon submicron spheres in application example 4 of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
Example 1
(1) Mixing 0.75mL of ammonia water (28% -30%) with 40mL of ethanol, adding 90mL of deionized water, and stirring gently at room temperature for 30min to obtain solution A. 0.5g dopamine hydrochloride was dissolved in 10mL deionized water and added to solution A, the color of the solution turned light brown immediately and gradually increased with increasing reaction time. After the reaction lasts for 30 hours, the solid product obtained by centrifugation is washed for 3 times by ethanol and deionized water and dried to obtain the nitrogen-doped carbon precursor.
(2) The nitrogen-doped carbon precursor was placed in a tube furnace and carbonized at 800 ℃ for 1h at a rate of 5 ℃/min in an argon atmosphere. The solid product obtained was taken up in 1:4, mixing the mixture with potassium hydroxide solid, heating to a low-temperature carbonization temperature of 400 ℃ at a heating rate of 5 ℃/min in an argon atmosphere, wherein the low-temperature carbonization time is 1h, and then heating to 800 ℃ and the high-temperature carbonization time is 1h. Cooling to room temperature after carbonization, washing the solid product with hydrochloric acid solution (1 mol/L) for 3 times, washing with water for 3 times, and drying to obtain the porous nitrogen-doped carbon submicron spheres.
(3) 0.1g of porous nitrogen-doped carbon submicron spheres were dispersed in 30mL of deionized water with ultrasound, and 0.1g of iron (III) acetate was added and stirring continued for 12h. The stirred solution was subjected to centrifugation to obtain a solid product, which was washed 3 times with ethanol and deionized water and dried. The dried solid product is processed in argon atmosphere at 5 ℃ for min -1 Is carbonized at 800 ℃ for 1 hour. After carbonization was completed, the mixture was cooled to room temperature, and the obtained solid product was mixed with sulfuric acid solution (0.5 mol/L) at a ratio of 1: and (3) mixing and stirring the mixture for 12 hours at room temperature to remove non-conjugated iron, washing the mixture for 3 times by using water, and drying the mixture to obtain the nitrogen-doped magnetic carbon submicron spheres.
(4) Acid solution of fulvic acid: the fulvic acid was dissolved with sodium hydroxide solution (0.1 mol/L) and the pH was adjusted to approximately 7.5, and then repeated 3 times through a 0.45 μm filter to obtain a soluble fulvic acid solution (2 mg/L). 0.1g of nitrogen-doped magnetic carbon submicron spheres were ultrasonically dispersed in 30mL of deionized water and mixed with 30mL of a fulvic acid solution for stirring for 12 hours. And after the reaction is finished, washing a solid product obtained by centrifugation for 3 times through ethanol and deionized water, and drying to obtain the fulvic acid composite nitrogen-doped magnetic carbon submicron spheres.
Example 2
The preparation method of the nitrogen-doped magnetic carbon submicron spheres in this example is the same as that in example 1, except that: the solubility of the soluble fulvic acid solution prepared in the step (4) is 5mg/L. 0.1g of nitrogen-doped magnetic carbon submicron spheres were ultrasonically dispersed in 30mL of deionized water and mixed with 30mL of a fulvic acid solution for stirring for 12 hours. And after the reaction is finished, washing a solid product obtained by centrifugation for 3 times by ethanol and deionized water, and drying to obtain the fulvic acid composite nitrogen-doped magnetic carbon submicron spheres, wherein the structural characterization of the obtained fulvic acid composite nitrogen-doped magnetic carbon submicron spheres is shown in figure 1.
Example 3
The preparation method of the nitrogen-doped magnetic carbon submicron spheres in this example is the same as that in example 1, except that: the solubility of the soluble fulvic acid solution prepared in the step (4) is 10mg/L. 0.1g of nitrogen-doped magnetic carbon submicron spheres were ultrasonically dispersed in 30mL of deionized water and mixed with 30mL of a fulvic acid solution for stirring for 12 hours. And after the reaction is finished, washing a solid product obtained by centrifugation for 3 times through ethanol and deionized water, and drying to obtain the fulvic acid composite nitrogen-doped magnetic carbon submicron spheres.
Comparative example 1
The porous nitrogen-doped carbon submicron spheres were prepared according to the methods of steps (1) and (2) in example 1.
Comparative example 2
The comparative example was prepared by the method of steps (1), (2) and (3) in example 1 to obtain nitrogen-doped magnetic carbon submicron spheres.
The porous nitrogen-doped carbon submicron spheres prepared in comparative example 1 and the nitrogen-doped magnetic carbon submicron spheres prepared in comparative example 2 were subjected to performance test, and the test results are shown in table 1.
TABLE 1 comparison of the Properties of carbon submicron spheres
Wherein "+" in the relative content of the active group is qualitatively indicated according to the content of the fulvic acid added in the process of preparing the material, the relative content of the active group increases along with the increase of the content of the fulvic acid, and when the relative content of the active group increases to a certain amount, the relative content of the active group decreases due to the decrease of the reactive site.
Table 1 shows a comparison of the properties of the carbon sub-micron spheres prepared in examples 1-3 and comparative examples 1-2. As shown in the table above, the fulvic acid composite nitrogen-doped magnetic carbon submicron spheres prepared in example 2 have the best performance, have proper carbon sphere size (800-900 nm), and have extremely large specific surface area (3000 m 2 /g~3500m 2 /g) and pore volume (2.17 cm 3 G), stronger magnetism and abundant carboxyl, amino, hydroxyl and other active groups.
Comparative example 1 is a nitrogen-doped carbon submicron sphere without iron (III) acetate loading and fulvic acid complexing, its specific surface area (1500 m 2 /g~2000m 2 /g) and pore volume (1.73 cm 3 /g) is smaller, lacks magnetism and has fewer active groups; comparative example 2 is nitrogen-doped magnetic carbon submicron spheres with no fulvic acid loading, the specific surface area (2000 m 2 /g~2500m 2 /g) and pore volume (1.89 cm 3 Per g), although significantly improved over comparative example 1, there was room for improvement, while the introduction of iron (iii) acetate made the material more magnetic. The concentration of fulvic acid in example 1 was 2mg/L, which was lower than that in example 2, so that the specific surface area of the prepared carbon submicron spheres (2500 m 2 /g~3000m 2 /g) and pore volume (2.03 cm 3 G) lower, less reactive groups; the fulvic acid concentration in example 3 was 10mg/L, which was too high compared with example 2, but rather occupied the reaction sites on the surface of the nitrogen-doped carbon spheres, and reacted with the nano-iron/maghemite supported by the nitrogen-doped carbon spheres, resulting in a specific surface area (2500 m 2 /g~3000m 2 /g) and pore volume (1.92 cm 3 Per g) is lower, reactive groups are reduced.
Application example 1
The fulvic acid composite nitrogen-doped magnetic carbon submicron spheres prepared in the embodiment 1 are applied to the restoration of the soil polluted by the antibiotics and the heavy metals, and the application method comprises the following steps: will be intended to repairThe soil polluted by heavy metals and antibiotics is pretreated, the particle size of the soil after pretreatment is 6nm, the pH value is 7, and the conductivity is 300 mu s cm -1 The water content is 50%, the concentration of antibiotics (tetracyclines, ciprofloxacin and sulfonamides) is 10mg/L, and the concentration of heavy metals (Pb (II) and Cu (II)) is 50mg/L.
Adding fulvic acid composite nitrogen doped magnetic carbon submicron spheres into the pretreated soil, uniformly mixing by adopting a turning machine after the addition, and curing for two weeks to obtain the restored soil, wherein the grain size of the soil after the turning is 2nm. The addition amount of the fulvic acid composite nitrogen-doped magnetic carbon submicron spheres is 5 weight percent of the soil polluted by the antibiotics and the heavy metals.
Application example 2
The fulvic acid composite nitrogen-doped magnetic carbon submicron spheres prepared in the example 2 are applied to the restoration of the soil polluted by the antibiotics and the heavy metals, and the application method is the same as that of the application example 1.
Application example 3
The fulvic acid composite nitrogen-doped magnetic carbon submicron spheres prepared in the embodiment 3 are applied to the restoration of the soil polluted by the antibiotics and the heavy metals, and the application method is the same as that of the application example 1.
Comparative example 1 was used
The application comparative example is that the porous nitrogen-doped carbon submicron spheres prepared in the comparative example 1 are applied to the restoration of the soil polluted by the antibiotics and the heavy metals, and the application method is the same as that of the application example 1.
Comparative example 2 was used
The application comparative example is that the nitrogen-doped magnetic carbon submicron spheres prepared in the comparative example 2 are respectively applied to the restoration of the soil polluted by the antibiotics and the heavy metals, and the application method is the same as that of the application example 1.
Comparative example 3 was used
The fulvic acid composite nitrogen-doped magnetic carbon submicron spheres prepared in the embodiment 3 are applied to the restoration of the soil polluted by the antibiotics and the heavy metals, and the application method comprises the following steps: and (3) pretreating the soil polluted by the heavy metal to be repaired and the antibiotics, wherein the particle size of the soil after pretreatment is 6nm, the pH value is 7, the conductivity is 300 mu s/cm, and the water content is 50%. Adding fulvic acid composite nitrogen doped magnetic carbon submicron spheres into the pretreated soil, uniformly mixing by adopting a turning machine after the addition, and curing for two weeks to obtain the restored soil, wherein the grain size of the soil after the turning is 2nm. The addition amount of the fulvic acid composite nitrogen-doped magnetic carbon submicron spheres is 2wt% of the soil polluted by the antibiotics and the heavy metals, the concentration of the antibiotics (tetracyclines, ciprofloxacin and sulfonamides) is 10mg/L, and the concentration of the heavy metals (Pb (II) and Cu (II)) is 50mg/L.
Comparative example 4 was used
The fulvic acid composite nitrogen-doped magnetic carbon submicron spheres prepared in the embodiment 3 are applied to the restoration of the soil polluted by the antibiotics and the heavy metals, and the application method comprises the following steps: and (3) pretreating the soil polluted by the heavy metal to be repaired and the antibiotics, wherein the particle size of the soil after pretreatment is 6nm, the pH value is 7, the conductivity is 300 mu s/cm, and the water content is 50%. Adding fulvic acid composite nitrogen doped magnetic carbon submicron spheres into the pretreated soil, uniformly mixing by adopting a turning machine after the addition, and curing for two weeks to obtain the restored soil, wherein the grain size of the soil after the turning is 2nm. The addition amount of the fulvic acid composite nitrogen-doped magnetic carbon submicron spheres is 10wt% of the soil polluted by the antibiotics and the heavy metals, the concentration of the antibiotics (tetracyclines, ciprofloxacin and sulfonamides) is 10mg/L, and the concentration of the heavy metals (Pb (II) and Cu (II)) is 50mg/L.
Table 2 comparison of adsorption (%) of typical antibiotics with heavy metals by application examples 1 to 3 and application comparative examples 1 to 4
Table 2 shows the comparison of the adsorption rates of typical antibiotics and heavy metals in application examples 1 to 3 and application comparative examples 1 to 4. As shown in the table above, application example 2 has the best effect of repairing the soil polluted by the antibiotics and the heavy metals, and the adsorption rate of the antibiotics and the heavy metals is more than 90%. Whereas nitrogen-doped carbon submicron spheres not subjected to iron (iii) acetate loading and fulvic acid complexing (application comparative example 1) and nitrogen-doped carbon submicron spheres not subjected to fulvic acid complexing (application comparative example 2) have lower adsorption rates for typical antibiotics TC, CIP and SDZ and heavy metals Pb (ii) and Cu (ii) in soil. The insufficient concentration (application example 1) and the too high concentration (application example 3) of the fulvic acid composite nitrogen-doped magnetic carbon submicron spheres in the preparation process also lead to lower adsorption rate of the prepared fulvic acid composite nitrogen-doped magnetic carbon submicron spheres on typical antibiotics TC, CIP and SDZ and heavy metals Pb (II) and Cu (II) in soil. This is consistent with the performance of its corresponding carbon sphere.
The adding amount of the fulvic acid composite nitrogen-doped magnetic carbon submicron spheres in the application comparative examples 3 and 4 is 2% and 10% of the soil compositely polluted by antibiotics and heavy metals. The insufficient application amount of the fulvic acid composite nitrogen-doped magnetic carbon submicron sphere (application of comparative example 3) leads to lower removal rate of antibiotics and heavy metals; and the carbon sphere is too high in application amount (comparative example 4 is applied), and agglomeration occurs due to magnetic attraction, so that the removal rate of antibiotics and heavy metals is also low. When the addition amount of the fulvic acid composite nitrogen-doped magnetic carbon submicron spheres is 5% of the soil polluted by the antibiotics and the heavy metals (application examples 1-3), the removal rate of the antibiotics and the heavy metals is higher, and the effect of repairing the soil polluted by the antibiotics and the heavy metals is best.
Application example 4
Under laboratory conditions, placing the soil after the repair in application example 2 in a magnetic field environment with the magnetic field strength of 2000GS, and recovering the fulvic acid composite nitrogen-doped magnetic carbon submicron spheres in the soil after the repair by the action of the magnetic field; the recovered fulvic acid composite nitrogen doped magnetic carbon submicron spheres are soaked in 0.1mol/L nitric acid solution, are added into 5mg/L soluble fulvic acid solution after being subjected to ultrasonic treatment for 15min, and react for 12h under the mixing condition. And after the reaction is finished, washing a solid product obtained by centrifugation for 3-5 times through ethanol and deionized water, and drying to obtain the regenerated fulvic acid composite nitrogen-doped carbon submicron spheres.
The regenerated fulvic acid composite nitrogen-doped carbon submicron spheres are applied to repairing and restoring the antibiotics and heavy metal composite polluted soil again according to the steps and conditions of application example 2, and then recycled and regenerated according to the steps, and the recycling and regeneration are carried out for five times, so that the removal rate of the antibiotics and the heavy metal after each regeneration is measured.
Fig. 2 is a graph comparing adsorption rates of typical antibiotics and heavy metals in soil after the fulvic acid composite nitrogen-doped carbon submicron spheres are regenerated for 0-5 times in the application example, and it can be seen from the graph that the adsorption rates of the fulvic acid composite nitrogen-doped carbon submicron spheres on the antibiotics and heavy metals in the soil are gradually reduced, but a good adsorption effect is still maintained, the adsorption rate is still above 80% after 3 times of regeneration, and the removal rate is still above 70% after 5 times of regeneration, so that the fulvic acid composite nitrogen-doped carbon submicron spheres prepared by the method have good repeated regeneration performance.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. The preparation method of the fulvic acid composite nitrogen-doped magnetic carbon submicron sphere is characterized by comprising the following steps of:
s1, mixing and reacting an ethanol water solution containing ammonia water with a dopamine solution to obtain a nitrogen-doped carbon precursor, and heating and carbonizing the nitrogen-doped carbon precursor in an inert atmosphere to obtain nitrogen-doped carbon submicron spheres;
s2, mixing the nitrogen-doped carbon submicron spheres with an alkaline substance, carbonizing in an inert atmosphere, and performing solid-liquid separation to obtain a solid phase, wherein the obtained solid phase is porous nitrogen-doped carbon submicron spheres;
s3, mixing and stirring the dispersion liquid of the porous nitrogen-doped carbon submicron spheres with iron (III) acetate, performing solid-liquid separation to obtain a solid product, and carbonizing the obtained solid product in an inert atmosphere to obtain the nitrogen-doped magnetic carbon submicron spheres;
s4, mixing and stirring the fulvic acid solution and the dispersion liquid of the nitrogen-doped magnetic carbon submicron spheres for reaction, and drying solid matters obtained by the reaction to obtain the fulvic acid composite nitrogen-doped magnetic carbon submicron spheres;
the concentration of the fulvic acid solution is 1 mg/L-10 mg/L.
2. The method of claim 1, wherein in step S1, at least one or more of the following conditions are satisfied:
the volume ratio of ammonia water, ethanol and water in the aqueous ethanol solution containing ammonia water is (0.5-2.0): (25-80): (80-150); the concentration of the ammonia water is 28-30wt%;
the concentration of the dopamine solution is 3-6wt%;
the mixing time is 18-36 h;
in the heating carbonization, the heating rate is 3-10 ℃/min, the carbonization temperature is 700-800 ℃, and the carbonization time is 1-2 h;
the inert atmosphere is inert gas such as argon and/or nitrogen.
3. The method of claim 1, wherein in step S2, at least one or more of the following conditions are satisfied:
the mass ratio of the nitrogen-doped carbon submicron spheres to the alkaline substance is (1-3): (2-10);
the alkaline substance is selected from potassium hydroxide and/or sodium hydroxide;
the carbonization process comprises the following steps: heating to the low-temperature carbonization temperature of 400-500 ℃ at a heating rate of 5-10 ℃/min, and the carbonization time of 1-2 h; then heating to a high-temperature carbonization temperature of 700-800 ℃ for 1-2 h;
the inert atmosphere is inert gas such as argon and/or nitrogen.
4. The method of claim 1, wherein in step S3, at least one or more of the following conditions are satisfied:
the mass ratio of the porous nitrogen-doped carbon submicron sphere to the iron (III) acetate is (0.1-0.5): (0.1 to 0.35);
the temperature rising rate in carbonization is 5-10 ℃/min, the carbonization temperature is 700-800 ℃, and the carbonization time is 1-2 h;
the mixing and stirring time is 12-24 hours.
5. The method of claim 1, wherein in step S4, at least one or more of the following conditions are satisfied:
the pH value of the fulvic acid solution is 7-8;
the solvent of the fulvic acid solution is sodium hydroxide solution with the concentration of 0.05mol/L to 0.2 mol/L;
the volume ratio of the mass of the nitrogen-doped magnetic carbon submicron spheres to the fulvic acid solution is (0.1-0.5): (20-30) g/mL.
6. The fulvic acid composite nitrogen-doped magnetic carbon submicron sphere obtained by the preparation method according to any one of claims 1 to 5, wherein the fulvic acid composite nitrogen-doped magnetic carbon submicron sphere comprises magnetic nitrogen-doped carbon submicron spheres and a fulvic acid and zero-valent iron/maghemite composite loaded on the surface of the magnetic nitrogen-doped carbon submicron sphere.
7. The fulvic acid composite nitrogen-doped magnetic carbon sub-microsphere according to claim 6, wherein the fulvic acid composite nitrogen-doped magnetic carbon sub-microsphere meets one or more of the following properties:
the particle size of the fulvic acid composite nitrogen-doped magnetic carbon submicron sphere is 100 nm-900 nm;
the magnetic strength is more than or equal to 25emg/g;
the surface is rich in a plurality of active functional groups.
8. The use of the fulvic acid composite nitrogen-doped magnetic carbon submicron spheres in the remediation of soil antibiotic and heavy metal composite pollution according to claim 6 or 7.
9. The application of claim 8, wherein the adding mass of the fulvic acid composite nitrogen-doped magnetic carbon submicron spheres is 4% -8% of the mass of the soil polluted by the antibiotics and the heavy metals.
10. The application of claim 8, wherein in the process of repairing soil, the curing time of the fulvic acid composite nitrogen-doped magnetic carbon submicron sphere and the composite polluted soil is more than or equal to 14d, and the soil repairing depth is 0-5 m.
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