CN113908835A - Preparation and application of active composite material based on non-free-radical efficient mineralization sulfonamide antibiotics - Google Patents
Preparation and application of active composite material based on non-free-radical efficient mineralization sulfonamide antibiotics Download PDFInfo
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- CN113908835A CN113908835A CN202111021954.7A CN202111021954A CN113908835A CN 113908835 A CN113908835 A CN 113908835A CN 202111021954 A CN202111021954 A CN 202111021954A CN 113908835 A CN113908835 A CN 113908835A
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- composite material
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- valent iron
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- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 229940123317 Sulfonamide antibiotic Drugs 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 230000033558 biomineral tissue development Effects 0.000 title description 8
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 46
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 46
- 230000005291 magnetic effect Effects 0.000 claims abstract description 37
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 21
- 150000003254 radicals Chemical class 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000002500 ions Chemical class 0.000 claims abstract description 10
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 6
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 6
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims abstract description 6
- 150000002505 iron Chemical class 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 4
- 239000002351 wastewater Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 230000002452 interceptive effect Effects 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 17
- 238000006731 degradation reaction Methods 0.000 abstract description 17
- 239000003054 catalyst Substances 0.000 abstract description 11
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000004021 humic acid Substances 0.000 abstract description 7
- 239000013543 active substance Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 230000001089 mineralizing effect Effects 0.000 abstract description 3
- 238000000967 suction filtration Methods 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 230000002431 foraging effect Effects 0.000 abstract 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 24
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 18
- 238000007254 oxidation reaction Methods 0.000 description 17
- 229960005404 sulfamethoxazole Drugs 0.000 description 16
- 230000003647 oxidation Effects 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 230000027756 respiratory electron transport chain Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000001994 activation Methods 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 150000001449 anionic compounds Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910001412 inorganic anion Inorganic materials 0.000 description 4
- -1 surface modification Chemical compound 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 3
- 229960004306 sulfadiazine Drugs 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- HQVFCQRVQFYGRJ-UHFFFAOYSA-N formic acid;hydrate Chemical compound O.OC=O HQVFCQRVQFYGRJ-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000013048 microbiological method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000007847 structural defect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003975 animal breeding Methods 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
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- 230000036541 health Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 244000052769 pathogen Species 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000002186 photoactivation Effects 0.000 description 1
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- 235000010344 sodium nitrate Nutrition 0.000 description 1
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Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- B01J35/33—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- 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
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
-
- 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
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Abstract
The invention belongs to the technical field of wastewater treatment, and discloses preparation and application of a catalyst based on non-free radical high-efficiency mineralized sulfonamide antibiotics. Sodium persulfate is catalyzed by the active composite material in aqueous solution to form a non-free radical active substance to participate in the process of efficiently mineralizing the sulfonamide antibiotics. Adding the carbon nano tube into an ethanol solution for ultrasonic dispersion, adding an iron salt solution for uniformly mixing, and adding a sodium borohydride solution; and adding sodium hydrosulfite solid, continuously stirring, standing for aging, performing suction filtration, cleaning, and freeze-drying to obtain black solid. The method has strong adaptability and anti-interference capability to pH, various ions and humic acid, the magnetic vulcanized nano zero-valent iron-carbon nano tube composite material can efficiently activate PDS, and the degradation rate of the magnetic vulcanized nano zero-valent iron-carbon nano tube composite material to sulfonamide antibiotics can reach 100%.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to preparation and application of an active composite material based on non-free-radical efficient mineralization of sulfonamide antibiotics.
Background
Sulfonamide Antibiotics (SAs), antibacterial agents synthesized by human engineering technology, have the characteristics of wide antibacterial spectrum, stable property, low production cost, simple and convenient use and the like, are widely applied to the industries of biological medicine and animal breeding, can effectively resist various pathogens, and have huge use amount. Unfortunately, the detection of some medical wastewater and wastewater of a farm reaches the level of mu g/L-mg/L. However, because of the special structure of coexistence of benzene ring and heterocycle, the sulfonamide antibiotics are not easy to degrade, also show lasting resistance to biodegradation and photodegradation, and can directly threaten human health through food chain enrichment. Therefore, it is imperative to seek methods for the efficient degradation of such persistent emerging pollutants.
The actual method for treating the sulfonamide antibiotic wastewater mainly comprises an adsorption method, a microbiological method, an electrochemical method, an advanced oxidation method and the like. Adsorption methods are poor in effect and cannot completely mineralize sulfonamide antibiotics; the microbiological method has low degradation efficiency, a plurality of influence factors and poor anti-interference capability; the electrochemical technology has high energy consumption and high relative degradation cost; the advanced oxidation techniques include mainly the fenton method, the fenton-like method, the ozone catalytic oxidation method, the photocatalytic oxidation method, and the persulfate catalytic oxidation method. Compared with hydrogen peroxide, ozone and artificial light sources, the persulfate has the advantages of low price, convenient transportation and more environmental protection. The persulfate advanced oxidation technology based on hydroxyl free radicals and sulfate free radicals shows good degradation efficiency on sulfonamide antibiotics, but still has the limitations that free radicals in actual water are easy to extinguish, the catalytic efficiency is to be improved, and the catalyst cannot be recycled. Therefore, the designed catalyst can activate persulfate to be efficiently converted into non-free radical (singlet oxygen and electron transfer) to further degrade small molecular organic acid, so as to achieve the purpose of efficiently mineralizing organic matters.
In comparison to conventional advanced oxidation techniques (AOPs), persulfates, mainly Peroxymonosulfate (PMS) and Peroxydisulfate (PDS), are considered to be more promising advanced oxidation techniques with their higher selectivity, half-life and redox potential. Compared with PMS, PDS has low cost, stable chemical property, convenient transportation and storage and is suitable for practical engineering application. However, the oxidation ability at normal temperature is relatively weak and the degradation ability of PDS is very limited, so PDS is generally activated by an external energy source or catalyst to oxidize organic contaminants. The activation modes of the PDS include thermal activation, alkali activation, photo activation, radiation activation, carbon material activation, transition metal activation, and the like.
As the second largest metal element contained in the earth's crust, zero-valent iron (nZVI), a typical easily available, low-toxic, environmentally friendly transition metal, which has an outstanding electron donating ability, it is considered to be highly efficient to activate PDS to produce active species. Unfortunately, the development of the iron alloy is limited by unstable factors such as easy agglomeration and easy oxidation of the zero-valent iron. Scientists have sought many ways to protect zero-valent iron, such as surface modification, metal modification, support modification.
To find a hiding place for the zero-valent iron. Carbon nanotubes, sp2The hexagonal network formed by the hybridized carbon atom units has the characteristics of hollow tubular shape, high conductivity, thermal stability and the like, and has good application prospect when being used as a catalyst carrier. Zero-valent iron sulfide is considered to be a layer of iron sulfide on the surface of a garment worn as zero-valent iron. The surface structure and the physicochemical property of the nZVI are changed through vulcanization, and the problems of easy aggregation, easy surface passivation and the like of the nZVI are solved while the high reducibility of the nZVI is maintained. The sulfuration state zero-valent iron shows better dispersibility than the oxidation state zero-valent iron, and can slow down the corrosion of the nZVI. Further, a ferrous sulfide layer (FeS) as a metal conductorx) Easily form delocalized electrons on the surface of S-nZVI, and promote the electrons to be transferred out from the zero-valent iron core.
Aiming at the problems, the invention discloses preparation and application of an active composite material based on non-free radical high-efficiency mineralization of sulfonamide antibiotics, wherein the carbon nano tube is used for loading and sulfur doping, so that the problems of easy agglomeration and easy oxidation of zero-valent iron and the like are solved bidirectionally, persulfate is synergistically activated to generate non-free radicals (singlet oxygen and electron transfer complex), and compared with the traditional free radical approach, the active composite material has stronger anti-interference capability, is capable of mineralizing the sulfonamide antibiotics more efficiently, and solves the problem of pollutant degradation deeply; in addition, the addition amount of the oxidant is low, the catalyst material is magnetic, and the problems that the catalyst is difficult to recover and the oxidation treatment cost is high are solved.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention provides a preparation method of a magnetic active composite material. The composite material has strong anti-interference capability on pH and various ions, has high degradation efficiency on sulfonamide antibiotics, and can keep high-efficiency organic matter mineralization capability.
The invention also aims to provide the application of the non-free radical-based high-efficiency mineralized sulfonamide antibiotics, and the magnetic vulcanized nano zero-valent iron-carbon nano tube composite material is applied to wastewater containing the sulfonamide antibiotics, so that the technical problems of high toxicity of the sulfonamide antibiotics and difficult degradation of the conventional water treatment technology are solved, and the problems of difficult recovery of a catalyst and large using amount of an oxidant are solved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an active composite material based on non-free radical high-efficiency mineralized sulfonamide antibiotics comprises the following specific steps:
s1, adding the carbon nano tube into an ethanol solution for ultrasonic dispersion, adding an iron salt solution for full and uniform mixing, adding a sodium borohydride solution into the mixed solution, and continuously stirring to obtain the magnetic nano zero-valent iron-carbon nano tube composite material;
s2, adding different doses of sodium hydrosulfite solid into the solution, and continuously stirring to obtain composite materials with different sulfur-iron ratios. And after the composite material is aged, performing suction filtration and cleaning, and finally performing freeze drying to obtain a black solid, namely the magnetic vulcanized nano zero-valent iron-carbon nano tube composite material. (ii) a
Preferably, the volume ratio of the mass of the carbon nano tube to the ethanol is (0.6-1.0): 40 g/mL.
Preferably, the iron salt solution is (0.6-1.2): 20 g/mL ferric chloride or ferrous sulfate solution.
Preferably, the sodium borohydride solution is (0.8-1.2): 50 g/mL.
Preferably, the solid dosage of the sodium hydrosulfite is (0.1-0.3): 100 g/mL.
Preferably, the aging time is 2-6 h; the freeze drying time is 6-8 h.
The invention provides a magnetic vulcanized nano zero-valent iron-carbon nano tube composite material prepared by the preparation method.
Further, the invention provides an application of the magnetic vulcanized nano zero-valent iron-carbon nano tube composite material in treating wastewater containing sulfonamide antibiotics. Specifically, the magnetic vulcanized nano zero-valent iron-carbon nano tube composite material is added into wastewater containing sulfonamide antibiotics, and sodium persulfate and interfering ions are added to carry out oscillation reaction.
Preferably, the adding amount of the magnetic vulcanized nano zero-valent iron-carbon nanotube composite material is 0.2 g/L; the initial pH value of the wastewater containing the sulfonamide antibiotics is 3-9; the concentration of the wastewater containing the sulfonamide antibiotics is 0.01-0.05 g/L; the interfering ions are Cl with the concentration of 50mmol/L-、NO3 -And HA; the concentration of the added sodium persulfate is 0.2-1 mmol/L.
In the magnetic vulcanized nano zero-valent iron-carbon nanotube composite material, the carbon nanotube is tubular, has a plurality of structural defects and is unique sp2The hexagonal network formed by the carbon units contains abundant C = O functional groups, so that the carbon structure itself becomes an active site for activating persulfate. Addition of persulfate, C = O group by S2O8 2-The formed hydrogen peroxide adduct is attacked and decomposed by intramolecular nucleophilic substitution of the alkoxy oxygen to form a dioxane intermediate. S2O8 2-Continuing to attack the dioxane intermediate to generate the non-base dioxane intermediateFree radical active species, singlet oxygen molecules, dominate the degradation of SMX. In addition, the carbon nano tube has large specific surface area and strong adsorption capacity, and is favorable for being combined with PDS to form a reactive complex on the surface to become another active site of the activated persulfate. The storage and transfer of electrons at the active site activates the stable sodium persulfate, thereby forming an electron transfer complex with strong oxidizing power. The vulcanized nano zero-valent iron accelerates electron transfer, and improves the electron transfer capability of a ternary system consisting of SMX, PDS and S-nZVI @ CNTs. Under the synergistic effect of the unique structure of the carbon nano tube and the co-doping of the vulcanized nano zero-valent iron, the persulfate is easier to activate, and the selectivity to organic pollutants is enhanced. Conventional radicals (e.g., hydroxyl radicals, sulfate radicals) are generally disturbed by pH and ions, and the range of applicability is limited. The magnetic vulcanized nano zero-valent iron-carbon nano tube composite material is based on an active substance (singlet oxygen) formed by catalyzing persulfate through non-free radicals&Electron transfer complex) and sulfanilamide antibiotics, so that the system has strong anti-interference capability on pH, various ions and humic acid, and can keep the mineralization capability of organic matters with high efficiency.
Compared with the prior art, the invention has the following beneficial effects:
1. the magnetic vulcanized nano zero-valent iron-carbon nanotube composite material has excellent specific surface area and porosity, numerous active groups (C = O, C-O-C) and abundant structural defects (sp = O, C-O-C)2Hybrid carbon), can efficiently activate PDS to remove sulfonamide antibiotics in water, and has extremely strong mineralization capability.
2. The magnetic vulcanized nano zero-valent iron-carbon nano tube composite material catalyzes persulfate to form a non-free radical active substance (singlet oxygen and electron transfer complex), the degradation rate of the composite material to sulfonamide antibiotics can reach 100% within 30min, the PDS dosage is small (0.2 mmol/L), the reaction time is short, and the mineralization degree is high.
3. The magnetic sulfurized nanoscale zero-valent iron-carbon nanotube composite material has stronger anti-interference capability on pH, various ions and humic acid based on a non-free radical active substance (singlet oxygen and electron transfer complex) formed by catalyzing persulfate, wherein the electron transfer complex and sulfanilamide antibiotics mainly react on the surface of the material and cannot be dissolved in a solvent and quenched by ions. In addition, the material is ferromagnetic in itself. Therefore, the catalytic oxidation system based on non-free radicals has strong anti-interference capability, can keep higher-efficiency organic matter oxidation capability and is convenient to recover catalyst materials.
Drawings
FIG. 1 is a C1s spectrum characterized by photoelectron spectroscopy of the material of example 1.
FIG. 2 shows the recycling of the composite material of example 1.
FIG. 3 is a graph showing the effect of different initial pH values on the degradation of sulfamethoxazole in example 3.
FIG. 4 is a graph showing the effect of interference of inorganic anions and humic acid on sulfamethoxazole degradation in example 4.
Detailed description of the preferred embodiments
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
Preparing a magnetic vulcanized nano zero-valent iron-carbon nano tube composite material:
1. adding 1.2 g of carbon nano tube into 80 mL of ethanol for ultrasonic dispersion, adding 20 mL of 0.2 mol/L ferric chloride solution, fully and uniformly mixing, adding 50 mL of 0.28 mol/L sodium borohydride solution into the mixed solution, and continuously stirring for 20 min.
2. Adding 0.1 g of sodium hydrosulfite into the solution, stirring for 30min, aging at 25 ℃ for 6 h, carrying out suction filtration and cleaning, and freeze-drying for 6 h to obtain a black solid which is a magnetic vulcanized nano zero-valent iron-carbon nano tube composite material;
identification of the magnetic vulcanized nano zero-valent iron-carbon nanotube composite material:
the elemental composition and valence state of the material were analyzed by X-ray photoelectron spectroscopy, and sp was found in 284.0, 284.8, 286.2 and 288.5 eV, respectively, as shown in FIG. 1 from the C1s spectrum2Hybrid carbon, C-C, C-O-C, and C = O structures, provide rich defect sites and functional groups for the reaction.
And analyzing the adsorption performance of the prepared material by adopting a full-automatic rapid specific surface and porosity analyzer through a nitrogen desorption adsorption experiment. As shown in table 1, which shows the specific surface area, pore diameter and pore volume of the activated carbon nanotube composite prepared in this example, it can be seen that the sulfurized nano zero-valent iron-carbon nanotube composite also has excellent specific surface area and porosity, and both sulfur doping and iron loading can enhance the adsorption performance of the material while enhancing the reduction performance of the material.
TABLE 1 ratio of specific surface area, porosity, pore volume characterized by the materials
Note: the BET of the full-automatic specific surface and porosity analyzer is the model number of the microphone ASAP2460, the degassing temperature is 300 ℃, the degassing time is 4 hours, and the analysis atmosphere is nitrogen.
The application of the magnetic vulcanized nano zero-valent iron-carbon nano tube composite material comprises the following steps:
taking sulfamethoxazole wastewater (0.01 g/L), adding sodium persulfate into the wastewater according to the concentration of 0.2 mmol/L, then adding 0.2g/L of the magnetic sulfurized nano zero-valent iron-carbon nano tube composite material prepared in the step 2 to start an oxidation reaction, and carrying out the reaction on a reciprocating shaking table at room temperature. Sampling is carried out at the time of 5, 10, 20, 30, 40 and 60 min, and the oxidation reaction of the samples sampled at each time point is stopped by taking ethanol as a quenching agent. Wherein sulfamethoxazole in the sample is detected by high performance liquid chromatography: the mobile phase is acetonitrile and 0.1% formic acid water (volume ratio is 2: 3), the flow rate is 0.6 mL/min, the column temperature is 35 ℃, and the detection wavelength is 254 nm.
The results show that the removal rates of sulfamethoxazole in the reaction systems at 5, 10, 20, 30, 40 and 60 min are respectively 58.5%, 71.2%, 91.2%, 97.7%, 98.4% and 100%.
Recycling the magnetic vulcanized nano zero-valent iron-carbon nano tube composite material:
standing the reaction solution, performing solid-liquid separation with a common magnet (as shown in FIG. 2), and removing the supernatant to recover and reuse the magnetic sulfurized nanoscale zero-valent iron-carbon nanotube composite material. The above application process is repeated, except that the added catalyst material is a recycled magnetic vulcanized nano zero-valent iron-carbon nano tube composite material.
The results show that the removal rate of sulfamethoxazole in 90 min can be respectively maintained at 85.2%, 70.9% and 67.8% after the system is circularly used for the first time, the second time and the third time. The strong magnetic property of the magnetic vulcanized nano zero-valent iron-carbon nano tube composite material helps the catalyst material to carry out solid-liquid separation and cyclic utilization, and the composite material shows good reusability and stability and exerts the available value of the material.
Example 2 Synthesis of magnetic sulfurized nanoscale zero-valent iron-carbon nanotube composites with different iron salt solutions
The difference from example 1 is that: taking sulfadiazine wastewater (0.02 g/L) in the application of the magnetic vulcanized nano zero-valent iron-carbon nano tube composite material, and adding sodium persulfate into the wastewater according to the concentration of 1 mmol/L, wherein the sulfadiazine is detected by high performance liquid chromatography: the mobile phase is acetonitrile and 0.1% formic acid water (volume ratio is 1: 4), the flow rate is 0.1 mL/min, the column temperature is 35 ℃, and the detection wavelength is 265 nm.
The results show that the removal rates of sulfadiazine in the reaction systems at 5 min, 10 min, 20 min, 30min, 40 min and 60 min are respectively 46.2%, 69.5%, 90.8%, 98.0%, 99.0% and 100%.
EXAMPLE 3 Effect of different initial pH on sulfamethoxazole degradation
The difference from example 1 is that: in the application process of the magnetic sulfurized nano zero-valent iron-carbon nano tube composite material, 5 parts of sulfamethoxazole wastewater (0.01 g/L) with initial pH values of 3, 5, 7, 9 and 11 are prepared, the concentration of sodium persulfate is added into each part of wastewater according to 0.2 mmol/L, and then 0.2g/L of the magnetic sulfurized nano zero-valent iron-carbon nano tube composite material is added. And (3) taking out water samples at the time of 5, 10, 20, 30, 40 and 60 min, and detecting the sulfamethoxazole concentration of the water samples.
The effect of different initial pH values on sulfamethoxazole degradation is shown in figure 3. The result shows that the removal rate of sulfamethoxazole is inhibited to a certain extent only when the pH is 11, and the catalytic system can efficiently degrade sulfamethoxazole within the pH range of 3-9.
Example 4 Effect of interference of inorganic anions and humic acid on sulfamethoxazole degradation
The difference from example 1 is that: in the application process of the magnetic sulfurized nano zero-valent iron-carbon nano tube composite material, 4 parts of sulfamethoxazole wastewater is prepared, sodium chloride (50 mmol/L), sodium nitrate (50 mmol/L) and sodium humate (20 mg/L) are respectively added, the concentration of sodium persulfate is added into each part of wastewater according to 1 mmol/L, and then 0.2g/L of the magnetic sulfurized nano zero-valent iron-carbon nano tube composite material is added. And (3) taking out water samples at the time of 5, 10, 20, 30, 40 and 60 min, and detecting the sulfamethoxazole concentration of the water samples.
FIG. 4 shows the effect of interference of inorganic anions and humic acid on sulfamethoxazole degradation. The result shows that the material has stronger adaptability to inorganic anions and humic acid and can adapt to water bodies containing interfering substances.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of an active composite material based on non-free radical high-efficiency mineralized sulfonamide antibiotics is characterized by comprising the following steps:
1) adding the carbon nano tube into an ethanol solution for ultrasonic dispersion, and then adding an iron salt solution for fully and uniformly mixing;
2) adding a sodium borohydride solution into the mixed solution;
3) adding sodium hydrosulfite solid into the mixed solution and continuously stirring;
4) and aging, filtering, cleaning, and freeze-drying to obtain black solid, namely the magnetic vulcanized nano zero-valent iron-carbon nanotube composite material.
2. The method according to claim 1, wherein the ratio of the mass of the carbon nanotube to the volume of ethanol in step 1) is (0.6 to 1.0): 40 g/mL; the ferric salt solution is (0.6-1.2): 20 g/mL ferric chloride or ferrous sulfate solution.
3. The method according to claim 1, wherein the sodium borohydride solution in step 2) is (0.8 to 1.2): 50 g/mL.
4. The preparation method according to claim 1, wherein the solid dosage of sodium dithionite in step 3) is (0.1-0.3): 100 g/mL.
5. The preparation method of claim 1, wherein the aging time in the step 4) is 2-6 h, and the freeze-drying time is 6-8 h.
6. The magnetic vulcanized nano zero-valent iron-carbon nanotube composite material obtained by the preparation method according to any one of claims 1 to 5.
7. The use of the magnetic sulfided nano zero-valent iron-carbon nanotube composite of claim 6 in the treatment of wastewater containing sulfonamide antibiotics.
8. The application of claim 7, wherein the magnetic sulfurized nano zero-valent iron-carbon nanotube composite material is added into wastewater containing sulfonamide antibiotics, and sodium persulfate and interfering ions are added for oscillation reaction under stirring.
9. The use of claim 8, wherein the magnetic sulfurized nano zero-valent iron-carbon nanotube composite is added in an amount of 0.2g/L of sulfonamide antibiotic wastewater.
10. The use according to claim 8 or 9, characterized in that the initial pH of the wastewater containing the sulfonamide antibiotics is adjusted to 3-9; the concentration of the wastewater containing the sulfonamide antibiotics is 0.01-0.05 g/L; the interfering ions are Cl with the concentration of 50mmol/L-、NO3 -And 20 mg/L HA; the concentration of the added sodium persulfate is 0.2-1 mmol/L.
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