CN115072854A - Method for removing triclosan in water by using nano zero-valent iron-ferroferric oxide composite material - Google Patents
Method for removing triclosan in water by using nano zero-valent iron-ferroferric oxide composite material Download PDFInfo
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- CN115072854A CN115072854A CN202210792085.6A CN202210792085A CN115072854A CN 115072854 A CN115072854 A CN 115072854A CN 202210792085 A CN202210792085 A CN 202210792085A CN 115072854 A CN115072854 A CN 115072854A
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- ferroferric oxide
- triclosan
- valent iron
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- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229960003500 triclosan Drugs 0.000 title claims abstract description 83
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 46
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 12
- XNCMOUSLNOHBKY-UHFFFAOYSA-H iron(3+);trisulfate;heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XNCMOUSLNOHBKY-UHFFFAOYSA-H 0.000 claims abstract description 11
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 11
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000006722 reduction reaction Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 25
- 238000002360 preparation method Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 7
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 238000004064 recycling Methods 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000002161 passivation Methods 0.000 abstract description 2
- 230000004044 response Effects 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 238000010998 test method Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 8
- 238000000605 extraction Methods 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 206010006187 Breast cancer Diseases 0.000 description 1
- 208000026310 Breast neoplasm Diseases 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 230000007035 DNA breakage Effects 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005907 cancer growth Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 210000003763 chloroplast Anatomy 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000003054 hormonal effect Effects 0.000 description 1
- 235000020256 human milk Nutrition 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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- 230000000717 retained effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 210000000130 stem cell Anatomy 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
-
- 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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
- C02F2101/36—Organic compounds containing halogen
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the field of water treatment, and particularly relates to a method for removing triclosan in water by using a nano zero-valent iron-ferroferric oxide composite material. Adding ferroferric oxide and ferric sulfate heptahydrate into water, slowly dropwise adding a sodium borohydride solution into the water, and carrying out reduction reaction under stirring to obtain the nano zero-valent iron-ferroferric oxide composite material nZVI-Fe 3 O 4 (ii) a Adding the nano zero-valent iron-ferroferric oxide composite material into water containing triclosan, and reacting to remove the triclosan. Mixing nZVI with Fe 3 O 4 The prepared composite material can prevent the oxidation and passivation of zero-valent iron in the reaction process and provide a new way for the transfer of electrons. At the same time, the user can select the desired position,Fe 3 O 4 has good magnetic response to external magnetic field, and is convenient for repeated utilization. The method adopts the nano zero-valent iron-ferroferric oxide composite material to remove the triclosan in the water for the first time, and can efficiently and completely remove the triclosan in the water in an environment-friendly way. Meanwhile, the recycling agent has a high-efficiency recycling rate convenient to recycle, has excellent economic benefits and has a wide application prospect.
Description
Technical Field
The invention belongs to the field of water treatment, and particularly relates to a method for removing triclosan in water by using a nano zero-valent iron-ferroferric oxide composite material.
Background
Triclosan (TCS) is a broad-spectrum bactericide of the type typically used in Pharmaceuticals and Personal Care Products (PPCPs), and is widely used in personal care products, household products, and pharmaceuticals. TCS has stable properties, and has the characteristics of hydrophobicity, lipophilicity, bioaccumulation, high toxicity and the like. TCS has high toxicity to various plants and organisms in water, particularly has obvious toxic effect on chloroplasts of algae, and can cause damage to the ecological environment of a water body. TCS is harmful to human body, can produce hormone effect in human breast cancer cells to promote the growth of cancer cells, and can cause DNA breakage of human stem cells to influence the synthesis of DNA. Therefore, TCS poses a non-negligible threat to animal, plant and human health. With the widespread use of TCS, the presence of TCS has been detected in rivers, lakes, seas, organisms, and even in human breast milk. TCS is difficult to remove in natural bodies of water and therefore needs to be controlled by establishing effective water treatment technologies.
Existing methods for TCS removal include adsorption, biological, and chemical oxidation. The adsorption method for removing TCS has low energy consumption and high adsorption speed, but cannot completely degrade TCS. The biological method for removing TCS has low cost, no secondary pollution, long time and strict variety and environmental conditions of microorganisms. The chemical oxidation method has high degradation efficiency, but has strict reaction conditions and higher treatment cost.
In view of the above, in order to remove TCS from water, it is necessary to find a convenient, effective, efficient and green water treatment method.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and provides a method for removing triclosan in water by using a nano zero-valent iron-ferroferric oxide composite material in order to remove toxic substances TCS in water and guarantee water environment safety.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a method for removing triclosan in water by using a nano zero-valent iron-ferroferric oxide composite material comprises the following steps:
(1) preparing a nano zero-valent iron-ferroferric oxide composite material;
(2) adding the nano zero-valent iron-ferroferric oxide composite material into water containing triclosan to obtain a mixed solution, and reacting to realize the removal of the triclosan.
Preferably, the method of the present invention is performed under the protection of an inert atmosphere, and more preferably, the inert atmosphere is at least one of nitrogen, argon and helium.
Preferably, the preparation of the nano zero-valent iron-ferroferric oxide composite material in the step (1) comprises the following steps:
(1.1) adding ferroferric oxide and iron sulfate heptahydrate into water to obtain a solution A;
(1.2) slowly dropwise adding a sodium borohydride solution into the solution A, and carrying out reduction reaction under stirring to obtain the nano zero-valent iron-ferroferric oxide composite material nZVI-Fe 3 O 4 。
Preferably, the preparation method of the ferroferric oxide in the step (1.1) comprises the following steps: dropwise adding ammonia water into water containing ferric trichloride hexahydrate and ferric sulfate heptahydrate, and stirring for reaction to obtain ferroferric oxide; more preferably, the concentration of ferric trichloride hexahydrate in water is 0.137mol/L, the concentration of ferric sulfate heptahydrate in water is 0.068mol/L, the molar ratio of ferric trichloride hexahydrate to ferric sulfate heptahydrate is 2:1, the concentration of ammonia water is 8mol/L, the volume ratio of ammonia water to water containing ferric trichloride hexahydrate and ferric sulfate heptahydrate is 1:8, the dropping speed of ammonia water is 5mL/min per minute, the stirring speed is 400r/min, the stirring time is 3h, and the stirring is started from the dropping; more preferably, Fe obtained by solid-liquid separation using a magnet after the reaction 3 O 4 The solid is nano-scale and is washed twice with deoxygenated water.
Preferably, the concentration of ferroferric oxide in the solution A in the step (1.1) is 0.1-1mol/L, and the concentration of ferric sulfate heptahydrate is 0.1-1 mol/L; more preferably, the concentration of the ferroferric oxide is 0.14mol/L, and the concentration of the ferric sulfate heptahydrate is 0.14 mol/L.
Preferably, the molar ratio of the ferroferric oxide to the iron sulfate heptahydrate in the step (1.1) is 5:1 to 1: 5.
Preferably, the concentration of the sodium borohydride solution in the step (1.2) is 0.05-0.5 mol/L.
Preferably, the molar ratio of the sodium borohydride to the iron sulfate heptahydrate in the step (1.2) is 2:1 to 4: 1.
Preferably, the dropping speed of the sodium borohydride solution in the step (1.2) is 5-10 mL/min.
Preferably, the stirring speed in the step (1.2) is 200-400r/min, and the reaction time is 2-4 h.
Preferably, after the reaction in the step (1.2) is finished, post-treatment is further carried out, and more preferably, the post-treatment comprises filtration, the filtration is carried out to obtain a reaction solution, and the solid is nZVI-Fe 3 O 4 More preferably, the filtration is vacuum filtration.
Preferably, in the step (1.2), the solid after filtration is washed with deoxygenated water for at least 2 times, and after washing with methanol for at least 1 time, the solid is freeze-dried by a freeze-dryer for at least 12h under vacuum.
Preferably, the removal of triclosan in step (2) is carried out under dark conditions. More preferably, the removal of triclosan is carried out by rotating the culture plate on a rotary incubator at a rotation speed of 45-300r/min in the absence of light.
Preferably, the initial concentration of triclosan in the water in the step (2) is 1000. mu.g/L, and more preferably 500. mu.g/L.
Preferably, the concentration of the nano zero-valent iron-ferroferric oxide composite material in the mixed solution in the step (2) is 1-20g/L, and more preferably 10 g/L.
Preferably, the reaction time in the step (2) is not less than 9h, more preferably 9-24h, and more preferably 12 h. When the reaction is carried out for 9 hours, the removal rate of the triclosan reaches 90 percent, and when the reaction time is further prolonged to 12 hours, the removal rate of the triclosan reaches 99.9 percent, so that the triclosan in the water can be efficiently and completely removed.
Preferably, the reaction in step (2) is carried out at room temperature, preferably at 25 ℃.
Preferably, the pH of the mixed solution in the step (2) is 1-10, and more preferably, the pH of the reaction mixed solution is 7.
The nano zero-valent iron (nZVI) has large specific surface area and strong reducing capability, and is an effective dehalogenation reducing agent. However, conventional nZVI systems are susceptible to oxidative deactivation. Ferroferric oxide (Fe) 3 O 4 ) Is a common iron oxide, which contains ferrous iron and ferric iron, and the iron ions in two valence states can be mutually converted. Fe 3 O 4 Is also a good semiconductor material, can conduct electricity, can transfer electrons, and can continuously maintain the activity of the nZVI. Fe 3 O 4 Has magnetism and can quickly realize solid-liquid separation. Mixing nZVI with Fe 3 O 4 The prepared composite material can prevent the oxidation and passivation of zero-valent iron in the reaction process and provide a new way for the transfer of electrons. At the same time, Fe 3 O 4 The composite material has good magnetic response to an external magnetic field, can be easily collected under the action of an external magnet, is convenient to recycle, and accords with the concept of green chemistry. Therefore, the application proposes the adoption of a zero-valent iron-ferroferric oxide composite material (nZVI-Fe) 3 O 4 ) A treatment method for removing TCS in water.
Compared with the prior art, the invention has the beneficial effects that: the invention provides a method for removing triclosan in water by using a nano zero-valent iron-ferroferric oxide composite material. Meanwhile, the recycling agent has a high-efficiency recycling rate convenient to recycle, has excellent economic benefits and has a wide application prospect.
Drawings
FIG. 1 shows nZVI and nZVI-Fe 3 O 4 XRD characterization pattern of (a);
FIG. 2 is nZVI-Fe 3 O 4 SEM characterization of (a);
FIG. 3 is nZVI-Fe 3 O 4 A VSM profile of (2);
FIG. 4 shows nZVI and Fe 3 O 4 、nZVI-Fe 3 O 4 The effect of removing TCS is compared to the figure.
Detailed Description
The technical solution of the present invention is further specifically described below by way of specific examples in conjunction with the accompanying drawings.
Example 1
The nZVI and the Fe are completed in an anaerobic glove box 3 O 4 、nZVI-Fe 3 O 4 The preparation of the composite material and the removal of TCS are realized in the nitrogen atmosphere in the whole test process.
The preparation method of nZVI is as follows: 7.67g of iron sulfate heptahydrate and 200mL of deoxygenated water are added into a beaker, 280mL of 0.05mol/L sodium borohydride solution is slowly added dropwise, and the mixture reacts for 3 hours under mechanical stirring. The solid was retained by suction filtration using a vacuum pump to obtain nZVI, which was washed twice with deoxygenated water and once with methanol.
Fe 3 O 4 The preparation method comprises the following steps: 7.45g of ferric trichloride hexahydrate and 3.835g of ferric sulfate heptahydrate are added into a beaker, 200mL of deoxygenated water is added, 25mL of 8mol/L ammonia water is slowly added dropwise, and the mixture is mechanically stirred for 3 hours to fully react (the rotating speed is 400 r/min). Using a vacuum pump to pump and filter and retain solids to obtain Fe 3 O 4 The cleaning is carried out twice by using deoxygenated water and once by using methanol.
The preparation method of the composite material comprises the following steps: 14.9g of ferric chloride hexahydrate and 7.67g of ferric sulfate heptahydrate are added into a beaker, 400mL of deoxygenated water is added, 50mL of 8mol/L ammonia water (about 5-10mL per minute) is slowly added dropwise, and the mixture is mechanically stirred for 3 hours to fully react (the rotating speed is 400 r/min). Fe obtained by solid-liquid separation using a magnet 3 O 4 The solids were washed three times with deoxygenated water. 7.67g of iron sulfate heptahydrate and 200mL of deoxygenated water are continuously added into a beaker, 280mL of 0.05mol/L sodium borohydride solution is slowly added dropwise, and the reaction is carried out for 3 hours under mechanical stirring. Using a vacuum pump to pump and filter and retain solid to obtain the nZVI-Fe 3 O 4 The cleaning is carried out twice by using deoxygenated water and once by using methanol. And (3) freezing and freeze-drying the obtained material for 12h in vacuum by using a freeze dryer, and transferring the freeze-dried material into an anaerobic box to grind and store powder for subsequent experiments after freeze-drying is finished.
The test method comprises the following steps: 0.08g of the composite was weighed into an 8mL brown extraction flask, 8mL deoxygenated water was added, and a TCS solution was added to give an initial concentration of 500. mu.g/L. After the bottle cap is tightly covered, the bottle cap is placed on a rotary incubator to rotate at the rotating speed of 45r/min in a dark place, samples are taken at regular time, and the samples are subjected to solid-liquid separation by a 5mL needle cylinder through a 0.7 mu m glass fiber filter membrane. The obtained water sample is analyzed and tested by high performance liquid chromatography.
From the experimental results, it can be known that: nZVI-Fe 3 O 4 Can effectively remove TCS in water. FIG. 1 shows nZVI and nZVI-Fe alone 3 O 4 The XRD characterization pattern of the material shows that the material is successfully synthesized. FIG. 2 is nZVI-Fe 3 O 4 The SEM representation chart shows that the particle diameter of the composite material particles is about 20nm, and the Fe is loaded by the granular nZVI 3 O 4 The surface is formed, the whole body is in an irregular blocky structure, the peripheral surface structure is relaxed, and a plurality of irregular pores are formed, so that the specific surface area of the nano composite material is increased. FIG. 3 is nZVI-Fe 3 O 4 The VSM representation chart shows that the material has strong magnetism, and can be separated from water through magnetic separation, thereby providing convenient conditions for recycling the material. FIG. 4 shows that nZVI alone is added in an amount of 10g/L and Fe alone 3 O 4 The dosage of the nZVI-Fe is 10g/L 3 O 4 When the reaction is carried out for 24 hours when the adding amount is 10g/L and the initial concentration of TCS is 500 mu g/L, the removal rate of nZVI to TCS is 53 percent, and Fe 3 O 4 The removal rate of TCS is 39%, nZVI-Fe 3 O 4 The removal rate of TCS can reach 99.9% in 12h, which indicates that the single nZVI and the single Fe are used 3 O 4 In contrast, nZVI-Fe 3 O 4 The effect of removing TCS is obviously improved.
Example 2
Completing nZVI-Fe in anaerobic glove box 3 O 4 The test procedure was carried out under nitrogen atmosphere. The test method is as follows: 0.04g, 0.06g, 0.08g and 0.1g of the composite material are respectively weighed and added into an 8mL brown extraction flask, 8mL deoxygenated water is added, and then TCS solution is added to make the initial concentration of the TCS solution be 500 mug/L. The bottle cap is covered and then placed in a rotary incubatorThe sample is periodically sampled by rotating the sample in the dark at the rotating speed of 45r/min, and the sampled samples are subjected to solid-liquid separation by a 5mL needle cylinder through a 0.7 mu m glass fiber filter membrane. The obtained water sample is analyzed and tested by high performance liquid chromatography.
Within the range of 2.5-12.5g/L, the TCS removal rate can be ensured to be higher than 90% in 24h, the TCS removal rate of the composite material is increased along with the increase of the material dosage, and when the material dosage is 10g/L, the TCS removal rate is higher than 99% in 12h reaction.
Example 3
Completing nZVI-Fe in anaerobic glove box 3 O 4 The test procedure was carried out under nitrogen atmosphere. The test method is as follows: 0.08g of the composite material was weighed into an 8mL brown extraction flask, 8mL deoxygenated water was added, and then TCS solution was added to give initial concentrations of 100, 500, 1000, 2000. mu.g/L, respectively. After the bottle cap is tightly covered, the bottle cap is placed on a rotary incubator to rotate at the rotating speed of 45r/min in a dark place, samples are taken at regular time, and the samples are subjected to solid-liquid separation by a 5mL needle cylinder through a 0.7 mu m glass fiber filter membrane. The obtained water sample is analyzed and tested by high performance liquid chromatography.
The initial concentration of TCS is 100-2000 mu g/L, the TCS can be basically removed within 24h, the removal rate of the composite material to the TCS is reduced along with the increase of the initial concentration of the TCS, and the removal rate of the TCS is still higher than 90% after 24h reaction when the initial concentration of the TCS is 2000 mu g/L.
Example 4
Completing nZVI-Fe in anaerobic glove box 3 O 4 The test procedure was carried out under nitrogen atmosphere. The test method is as follows: 0.08g of the composite was weighed into an 8mL brown extraction flask, 8mL deoxygenated water was added, and a TCS solution was added to bring the initial concentration to 500. mu.g/L. Covering the bottle cap tightly, placing on a rotary incubator, rotating at rotation speeds of 15, 30, 45 and 60r/min in a dark place, sampling at regular time, and performing solid-liquid separation on the samples with a 5mL needle cylinder through a 0.7 mu m glass fiber filter membrane. The obtained water sample is analyzed and tested by high performance liquid chromatography.
The TCS can be basically removed within 24h within the range of the rotating speed of 15-60r/min, the removing rate of the composite material to the TCS is increased along with the increase of the rotating speed, and when the rotating speed is more than 45r/min, the TCS removing rate is higher than 99% in 12h of reaction. Example 5
Completing nZVI-Fe in anaerobic glove box 3 O 4 The test procedure was carried out under nitrogen atmosphere. The test method is as follows: 0.08g of the composite material was weighed into an 8mL brown extraction flask, 8mL deoxygenated water was added, the pH of the solution was adjusted to 3, 5, 7, 9, 11 with 1mol/L HCl or NaOH, and TCS solution was added to give an initial concentration of 500. mu.g/L. After the bottle cap is tightly covered, the bottle cap is placed on a rotary incubator to rotate at the rotating speed of 45r/min in a dark place, samples are taken at regular time, and the samples are subjected to solid-liquid separation by a 5mL needle cylinder through a 0.7 mu m glass fiber filter membrane. The obtained water sample is analyzed and tested by high performance liquid chromatography.
With the increase of the pH value of the solution, the removal rate of the composite material to TCS is reduced, the removal rate of TCS is higher than 99% when the composite material reacts for 12h within the range of pH 3-7, and the removal rate of TCS is higher than 90% when the composite material reacts for 24h within the range of pH 3-11, so that the material can ensure a good removal effect of TCS within a large pH range.
Example 6
Completing nZVI-Fe in anaerobic glove box 3 O 4 The test procedure was carried out under nitrogen atmosphere. The test method is as follows: 0.08g of the composite was weighed into an 8mL brown extraction flask, 8mL deoxygenated water was added, and a TCS solution was added to give an initial concentration of 500. mu.g/L. After the bottle cap is tightly covered, the bottle cap is placed on a rotary incubator to rotate at the rotating speed of 45r/min in a dark place. After 24 hours of reaction, the particles were subjected to solid-liquid separation using a magnet. The obtained water sample is subjected to solid-liquid separation by a 5mL syringe through a 0.7 mu m glass fiber filter membrane, and is analyzed and tested by high performance liquid chromatography. And repeatedly washing the obtained solid material by using deoxygenated water and absolute ethyl alcohol, freeze-drying for 12h, and carrying out a triclosan removal test on the recovered material according to experimental conditions. After 5 passes of nZVI-Fe 3 O 4 The TCS removing effect is slightly reduced along with the increase of the recovery times in the recovery and TCS removing tests, and the TCS removing rate of the composite material is still higher than that of the composite material after the reaction is carried out for 5 times and 12 hours90% indicating nZVI-Fe 3 O 4 Good stability, easy recovery and repeated use.
The above-described embodiments are merely preferred embodiments of the present invention, which is not intended to be limiting in any way, and other variations and modifications are possible without departing from the scope of the invention as set forth in the appended claims.
Claims (10)
1. A method for removing triclosan in water by using a nano zero-valent iron-ferroferric oxide composite material is characterized by comprising the following steps:
(1) preparing a nano zero-valent iron-ferroferric oxide composite material;
(2) adding the nano zero-valent iron-ferroferric oxide composite material into water containing triclosan to obtain a mixed solution, and reacting to realize the removal of the triclosan.
2. The method for removing triclosan in water by using the nano zero-valent iron-ferroferric oxide composite material according to claim 1, wherein the preparation of the nano zero-valent iron-ferroferric oxide composite material in the step (1) comprises the following steps:
(1.1) adding ferroferric oxide and iron sulfate heptahydrate into water to obtain a solution A;
(1.2) slowly dropwise adding a sodium borohydride solution into the solution A, and carrying out reduction reaction under stirring to obtain the nano zero-valent iron-ferroferric oxide composite material nZVI-Fe 3 O 4 。
3. The method for removing triclosan in water by using the nano zero-valent iron-ferroferric oxide composite material according to claim 2, wherein the preparation method of the ferroferric oxide in the step (1.1) comprises the following steps: and (3) dropwise adding ammonia water into water containing ferric trichloride hexahydrate and ferric sulfate heptahydrate, and stirring for reacting to obtain ferroferric oxide.
4. The method for removing triclosan in water by using the nano zero-valent iron-ferroferric oxide composite material according to claim 2, wherein the concentration of the ferroferric oxide in the solution A in the step (1.1) is 0.1-1mol/L, and the concentration of the iron sulfate heptahydrate is 0.1-1 mol/L.
5. The method for removing triclosan in water by using the nano zero-valent iron-ferroferric oxide composite material according to claim 2, wherein the concentration of the sodium borohydride solution in the step (1.2) is 0.05-0.5 mol/L.
6. The method for removing triclosan in water by using the nano zero-valent iron-ferroferric oxide composite material according to claim 2, wherein the molar ratio of the sodium borohydride to the ferric sulfate heptahydrate in the step (1.2) is 2:1 to 4: 1.
7. The method for removing triclosan in water by using the nano zero-valent iron-ferroferric oxide composite material according to claim 2, wherein the dropping speed of the sodium borohydride solution in the step (1.2) is 5-10 mL/min.
8. The method for removing triclosan in water according to claim 1, wherein the initial concentration of triclosan in water in step (2) is 100-1000 μ g/L.
9. The method for removing triclosan in water by using the nano zero-valent iron-ferroferric oxide composite material according to claim 1, wherein the concentration of the nano zero-valent iron-ferroferric oxide composite material in the mixed solution in the step (2) is 1-20 g/L.
10. The method for removing triclosan in water by using the nano zero-valent iron-ferroferric oxide composite material according to claim 1, wherein the pH of the mixed solution in the step (2) is 1-10, and the reaction time is not less than 9 h.
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