CN111167400A - Application of modified iron-based functional material in heavy metal pollution remediation - Google Patents
Application of modified iron-based functional material in heavy metal pollution remediation Download PDFInfo
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- CN111167400A CN111167400A CN202010054398.2A CN202010054398A CN111167400A CN 111167400 A CN111167400 A CN 111167400A CN 202010054398 A CN202010054398 A CN 202010054398A CN 111167400 A CN111167400 A CN 111167400A
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- 239000000463 material Substances 0.000 title claims abstract description 179
- 150000002505 iron Chemical class 0.000 title claims abstract description 88
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 44
- 238000005067 remediation Methods 0.000 title claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 145
- 238000001179 sorption measurement Methods 0.000 claims abstract description 67
- 229910052742 iron Inorganic materials 0.000 claims abstract description 59
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 54
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 30
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 30
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract description 30
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims abstract description 30
- 239000007864 aqueous solution Substances 0.000 claims abstract description 25
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims abstract description 18
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 18
- 230000010355 oscillation Effects 0.000 claims abstract description 17
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 16
- 231100000719 pollutant Toxicity 0.000 claims abstract description 16
- 244000005700 microbiome Species 0.000 claims abstract description 13
- 229940093476 ethylene glycol Drugs 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 3
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 26
- 230000001954 sterilising effect Effects 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 239000002244 precipitate Substances 0.000 claims description 23
- 241000193385 Geobacillus stearothermophilus Species 0.000 claims description 17
- 241000222122 Candida albicans Species 0.000 claims description 16
- 229940095731 candida albicans Drugs 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 241000228245 Aspergillus niger Species 0.000 claims description 14
- 238000004659 sterilization and disinfection Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000001888 Peptone Substances 0.000 claims description 13
- 108010080698 Peptones Proteins 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 235000019319 peptone Nutrition 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 12
- 238000007789 sealing Methods 0.000 claims description 12
- 239000012047 saturated solution Substances 0.000 claims description 8
- 238000010304 firing Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 2
- 238000011109 contamination Methods 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 13
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000005389 magnetism Effects 0.000 abstract description 2
- 230000007847 structural defect Effects 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 description 23
- 238000010438 heat treatment Methods 0.000 description 22
- 239000010949 copper Substances 0.000 description 20
- 238000001000 micrograph Methods 0.000 description 17
- 238000009826 distribution Methods 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000002336 sorption--desorption measurement Methods 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000001580 bacterial effect Effects 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
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- 238000002360 preparation method Methods 0.000 description 3
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- 239000000126 substance Substances 0.000 description 2
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 241000770536 Bacillus thermophilus Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- OFHCOWSQAMBJIW-AVJTYSNKSA-N alfacalcidol Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C\C=C1\C[C@@H](O)C[C@H](O)C1=C OFHCOWSQAMBJIW-AVJTYSNKSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
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- 238000005342 ion exchange Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000005408 paramagnetism Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 235000010204 pine bark Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Chemical & Material Sciences (AREA)
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- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
Abstract
The invention belongs to the field of environmental management, and particularly relates to application of a modified iron-based functional material in heavy metal pollution remediation. The modified iron-based functional material is prepared by taking ferric chloride hexahydrate, ethylene glycol, anhydrous sodium acetate, diethylenetriamine and sodium dodecyl sulfate as raw materials and inoculating microorganisms through ultraviolet rays, placing the modified iron-based functional material in an aqueous solution containing heavy pollutants, adjusting the pH value to 3-6, and placing the modified iron-based functional material in a constant temperature oscillator with the temperature of 25 ℃ and the rotating speed of 170 ℃ for oscillation for 3-50 min. According to the invention, the iron-based functional material is modified by microorganisms, so that the pore structure of the adsorption material can be improved, an incompletely reacted intermediate is etched, the structural defects are reduced, the intermediate becomes a charge trap site, and the intermediate has the characteristic of strong magnetism.
Description
Technical Field
The invention belongs to the field of environmental management, and particularly relates to application of a modified iron-based functional material in heavy metal pollution remediation.
Background
The heavy metal wastewater has the characteristics of wide sources and difficult treatment, and is always a difficult problem in the field of water treatment. In order to reduce the harm of heavy metal pollution, a great deal of research has been carried out on the treatment of heavy metal wastewater at home and abroad, at present, the treatment method of heavy metal wastewater mainly comprises a complexation method, an alkali precipitation method, an oxidation-reduction method, an ion exchange method, an adsorption method and the like, among a plurality of treatment methods, the adsorption method has the characteristics of high efficiency, energy conservation, recycling and the like, and is widely applied to the treatment of wastewater by people, in the application of the adsorption method, the selection of an adsorbent is particularly important, at present, some materials can be used for the research of removing different heavy metal ions in water, such as pine bark (a sewage heavy metal ion adsorbent disclosed by Chinese patent CN105642252A and a preparation method thereof), fly ash (an industrial wastewater heavy metal removal method disclosed by Chinese patent CN 1194238A), red mud (a stabilization method of phosphorus and heavy metals in sludge of a sewage treatment plant disclosed by Chinese patent CN 102234167A) and the like, however, these adsorbents have the characteristics of low adsorption stability, low adsorption rate, complex preparation process, difficult regeneration and the like. The magnetic nano-disc and the method for treating heavy metal sewage by using the same disclosed in the chinese patent CN105056890A are characterized in that the prepared magnetic nano-disc is subjected to surface amino modification to improve the adsorption capacity of heavy metal ions, so that the magnetic nano-functional material becomes one of the most attractive adsorption materials at home and abroad at present due to its unique paramagnetism, good biocompatibility, higher adsorption capacity, recyclability and other advantages.
Disclosure of Invention
In order to solve the problems that heavy metal ions such as copper and cadmium in the wastewater cannot be degraded by microorganisms due to persistence, concealment and high toxicity, the invention provides an application of a modified iron-based functional material in repairing heavy metal pollution.
In order to achieve the purpose, the invention adopts the following scheme:
application of modified iron-based functional material in heavy metal pollution remediation, specifically, application of modified iron-based functional material in adsorption of Cu in heavy metal polluted water2+And Cd2+(ii) a The modified iron-based functional material is prepared by taking ferric chloride hexahydrate, ethylene glycol, anhydrous sodium acetate, diethylenetriamine and sodium dodecyl sulfate as raw materials, reacting to prepare the iron-based functional material, and inoculating microorganisms.
Further, the modified iron-based functional material adsorbs Cu2+And Cd2+The method comprises the following specific steps: and (3) placing the modified iron-based functional material in an aqueous solution containing heavy pollutants, adjusting the pH to 3-6, and placing the modified iron-based functional material in a constant-temperature oscillator at the temperature of 25 ℃ and the rotating speed of 170 ℃ for oscillation for 3-50 min.
Further, the pH was 5.38 and the time of shaking was 30 min.
Further, the preparation process of the modified iron-based functional material is as follows: step A, putting ferric chloride hexahydrate into a beaker, adding ethylene glycol, stirring for 30-40 min, adding anhydrous sodium acetate, diethylenetriamine and sodium dodecyl sulfate, stirring until the anhydrous sodium acetate, diethylenetriamine and sodium dodecyl sulfate are completely dissolved, transferring the mixture into an autogenous pressure reaction kettle with a polytetrafluoroethylene lining, sealing, reacting at the constant temperature of 180-220 ℃ for 1.8-2.2 h, cooling to room temperature, washing, centrifuging and drying to obtain an iron-based functional material; and step B, mixing the peptone and the iron-based functional material, adding water for sterilization, inoculating microorganisms, oscillating at constant temperature, taking the precipitate, drying and firing at high temperature to obtain the modified iron-based functional material.
Further, in the step A, the mass ratio of the sodium dodecyl sulfate to the anhydrous sodium acetate to the ferric chloride hexahydrate is 5: 40: 17, the ethylene glycol: the volume ratio of diethylenetriamine is 8-10: 1.
further, the washing in the step a is alternately washing with deionized water and absolute ethyl alcohol, wherein the deionized water: the proportion of the absolute ethyl alcohol is 2-3: 5 to 7.
Further, the centrifugation in the step A is carried out for 5min at 4000r/min, and the drying temperature is 60-70 ℃.
Further, the microorganism in the step B is Aspergillus niger, Candida albicans or Bacillus stearothermophilus, and the ratio of the iron-based functional material to the microorganism saturated solution is 125 g: 1 mL. Iron-based functional material: peptone: 1g of water: 1 g: 100mL, the sterilization temperature is 121 ℃, and the sterilization time is 30 min.
Further, the oscillation condition in the step B is oscillation for 2-6 days at 37 ℃ at the rotating speed of 170 r/min. The drying temperature is 75-85 ℃, and the high-temperature firing process is as follows: and (3) placing the dried precipitate in a crucible, heating to 550 ℃ at the heating rate of 5 ℃/min, and burning for 3-5 h.
Detecting the prepared iron-based functional material and the modified iron-based functional material, and recording the morphology of the magnetic microspheres by a Scanning Electron Microscope (SEM) to reveal the surface morphology of the sample; the XRD results indicate the phase and chemical composition of the synthesized material. According to the standard card (JCPDS No. 39-1346), the peak intensity and width represent a clear peak from the XRD image, which is the crystal structure of the magnetic material; the BET results show: the obvious hysteresis loop shows that a mesoporous structure exists, and both bacterial etching samples and non-bacterial etching samples present typical Langmuir IV curves under the same condition, which indicates that the obtained bacterial etching material is a mesoporous material.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the iron-based functional material is prepared by using sodium dodecyl sulfate, anhydrous sodium acetate, ferric chloride hexahydrate, ethylene glycol and diethylenetriamine, and the aspergillus niger, candida albicans and bacillus stearothermophilus are used for modifying the iron-based functional material, so that microorganisms are widely distributed in the environment, are easy to culture, have high growth and propagation speed, reduce the consumption of chemicals, are environment-friendly, have low production cost and can be used for batch production. And the microorganisms can improve the pore structure of the adsorbing material, etch the incompletely-reacted intermediate, reduce the structural defects, and enable the intermediate to become a charge trap site, and meanwhile, the modified iron-based functional material has the characteristic of strong magnetism, so that the efficiency of adsorbing and removing heavy metals is improved, the highest adsorption rate of copper ions and cadmium ions exceeds 99 percent, even reaches 100 percent, and the modified iron-based functional material can be widely applied.
Drawings
FIG. 1 is a scanning electron microscope image of the Fe-based functional material prepared in example 1;
FIG. 2 is a nitrogen adsorption-desorption curve of the iron-based functional material prepared in example 1;
FIG. 3 is a pore size distribution curve of the iron-based functional material prepared in example 1;
FIG. 4 is a scanning electron microscope image of the modified Fe-based functional material prepared in example 1;
FIG. 5 is a scanning electron microscope image of the Fe-based functional material prepared in example 2;
FIG. 6 is a nitrogen adsorption-desorption curve of the iron-based functional material prepared in example 2;
FIG. 7 is a pore size distribution curve of the iron-based functional material prepared in example 2;
FIG. 8 is a comparative XRD pattern of the Fe-based functional materials prepared in examples 1 and 2;
FIG. 9 is FT-IR spectra of the iron-based functional materials prepared in examples 1 and 2;
FIG. 10 is a scanning electron microscope image of the modified Fe-based functional material prepared in example 2;
FIG. 11 is a scanning electron microscope image of the modified Fe-based functional material prepared in example 3;
FIG. 12 is a scanning electron micrograph of the iron-based functional material prepared in example 7;
FIG. 13 is a scanning electron microscope image of the modified Fe-based functional material prepared in example 7;
FIG. 14 is a scanning electron microscope image of the modified Fe-based functional material prepared in example 8;
FIG. 15 is a scanning electron microscope image of the modified Fe-based functional material prepared in example 9;
FIG. 16 is a drawing showing nitrogen desorption of the iron-based functional material prepared in example 10;
FIG. 17 is a pore size distribution diagram of the iron-based functional material prepared in example 10;
FIG. 18 is a graph of pore volume of the iron-based functional material prepared in example 10;
fig. 19 is an XRD pattern of the iron-based functional material prepared in example 10;
FIG. 20 is a graph of adsorption capacity versus pH for the modified Fe-based functional material prepared in example 10;
FIG. 21 is a graph showing the relationship between the adsorption capacity and the dosage of the modified Fe-based functional material prepared in example 11;
FIG. 22 is a graph of adsorption capacity versus oscillation time for the modified Fe-based functional material prepared in example 12;
FIG. 23 is a graph showing the relationship between the adsorption capacity and the heavy metal concentration of the modified Fe-based functional material prepared in example 13
Detailed Description
Example 1
Taking 10.8g of ferric chloride hexahydrate and 320ml of ethylene glycol, magnetically stirring for 30min at room temperature, adding 16g of anhydrous sodium acetate, 40ml of diethylenetriamine and 2g of sodium dodecyl sulfate, stirring until the anhydrous sodium acetate, the diethylenetriamine and the sodium dodecyl sulfate are completely dissolved, transferring the mixture into a self-pressure reaction kettle containing a polytetrafluoroethylene lining, sealing the reaction kettle, reacting in a constant-temperature oven at 160 ℃ for 2h, taking out the reaction kettle, and naturally cooling to room temperature. Washing with deionized water and absolute ethyl alcohol, centrifuging at 4000r/min for 5min, taking the precipitate, and drying in a thermostat at 60 ℃ to obtain the iron-based functional material, wherein fig. 1 is a scanning electron microscope image of the iron-based functional material prepared in the embodiment: the iron-based functional material has uniform grain distribution, rough surface and slight curl at the edge. The overall appearance is good, the particle size is about 200nm, and the thickness is about 10 nm; fig. 2 is a nitrogen adsorption-desorption curve of the iron-based functional material prepared in this example: the adsorption-desorption isothermal curve of the material belongs to type IV; fig. 3 is a pore size distribution curve of the iron-based functional material prepared in this example: the surface area of the iron-based functional material is about 104m2Per g, pore volume about 0.45cm3G, pore size of about 16.4 nm: .
Placing 2.5g of peptone and 2.5g of the prepared iron-based functional material in a conical flask, adding 250ml of water, placing in a high-pressure steam sterilization pot, sterilizing at 121 ℃ for 30min, inoculating 20 mu L of saturated solution of Bacillus stearothermophilus, oscillating at constant temperature of 170r/min and oscillating at 37 ℃ for 2 days. Drying at 75 ℃, placing the dried precipitate in a crucible, heating to 550 ℃ at a heating rate of 5 ℃/min, and firing for 3 hours to obtain the modified iron-based functional material, wherein fig. 4 is a scanning electron microscope image of the modified iron-based functional material prepared in the embodiment: the modified iron-based functional material has the advantages of uneven grain distribution, rough surface and good overall appearance.
0.06g of the Bacillus stearothermophilus modified iron-based functional material is put into an aqueous solution containing heavy metal pollutants (the prepared solution and the non-polluted water are all prepared), the pH value is adjusted to 5.38, the solution is oscillated in a constant temperature oscillator for 35min, and the adsorbed Cu is measured2+、Cd2+The concentrations of (A) are shown in Table 1.
TABLE 1 Cu before and after adsorption of the modified Fe-based functional material prepared in example 12+、Cd2+In an amount of
As can be seen from the above table, the modified Fe-based functional material of Bacillus stearothermophilus prepared in this example is Cu2+The highest adsorption rate of the catalyst can reach 96.9 percent, and the catalyst can adsorb Cd2+The highest adsorption rate can reach 95.98%.
Example 2
Taking 10.8g of ferric chloride hexahydrate and 320ml of ethylene glycol, magnetically stirring for 30min at room temperature, adding 16g of anhydrous sodium acetate, 40ml of diethylenetriamine and 2g of sodium dodecyl sulfate, stirring until the anhydrous sodium acetate, the diethylenetriamine and the sodium dodecyl sulfate are completely dissolved, transferring the mixture into a self-pressure reaction kettle containing a polytetrafluoroethylene lining, sealing, reacting in a constant-temperature oven at 220 ℃ for 3h, taking out, and naturally cooling to room temperature. Washing with deionized water and absolute ethyl alcohol, centrifuging for 5min at 4000r/min, and drying the precipitate in a thermostat at 65 ℃ to obtain the iron-based functional material, wherein fig. 5 is a scanning electron microscope image of the iron-based functional material prepared in the embodiment, and fig. 6 is a nitrogen adsorption-desorption curve of the iron-based functional material prepared in the embodiment; FIG. 7 is a pore size distribution curve of the Fe-based functional material prepared in this example; fig. 8 is an XRD comparison pattern of the iron-based functional materials prepared in example 1 and this example: the XRD patterns of the iron-based functional materials prepared in example 1 and this example showed five and six sharp diffraction peaks, respectively. The five diffraction peaks 2 θ of example 1 were 14.298 °, 27.215 °, 38.071 °, 46.957 ° and 60.149 °, respectively. The iron-based functional material prepared in this exampleThe six diffraction peak values 2 theta of the material are 30.23 deg., 35.59 deg., 43.29 deg., 53.68 deg., 62.79 deg., and 74.23 deg., respectively. Fig. 9 is a FT-IR spectrum of the iron-based functional material prepared in example 1 and this example: the IR absorption spectrum of the material of example 1 was 3440cm-1The wider absorption peak in the vicinity is a strong stretching vibration of the surface of the material of example 1. At 2927cm-1Is located at an asymmetric telescopic vibration absorption peak at 2857cm-1The position is a symmetric telescopic vibration absorption peak at 1635cm-1Bending vibration of 1578cm-1Has a symmetrical vibration absorption peak at 1445cm-1Is at an asymmetric vibration absorption peak at 1124cm-1Is the vibration peak. The IR absorption spectrum of the iron-based functional material prepared in the example is obviously different from that of the material prepared in the example 1, which shows that the temperature rise has an influence on the sample and is 545cm-1The peak at (b) is an absorption peak of stretching vibration in the iron-based functional material prepared in this example.
Placing 2.5g of peptone and 2.5g of the iron-based functional material prepared above in a conical flask, adding 250ml of water, placing in a high pressure steam sterilization pot, sterilizing at 121 deg.C for 30min, inoculating Bacillus stearothermophilus with 20 μ L of saturated solution, oscillating at constant temperature of 170r/min, and oscillating at 37 deg.C for 4 days. Drying at 75 ℃, placing the dried precipitate in a crucible, heating to 550 ℃ at a heating rate of 5 ℃/min, and burning for 3h to obtain the modified iron-based functional material, wherein fig. 10 is a scanning electron microscope image of the modified iron-based functional material prepared in the embodiment.
0.06g of the Bacillus stearothermophilus modified iron-based functional material is put into an aqueous solution containing heavy metal pollutants (the prepared solution and the non-polluted water are all prepared), the pH value is adjusted to 5.38, the solution is oscillated in a constant temperature oscillator for 30min, and the adsorbed Cu is measured2+、Cd2+The concentrations of (A) are shown in Table 2.
TABLE 2 Cu before and after adsorption of the modified Fe-based functional material prepared in example 22+、Cd2+In an amount of
As can be seen from the above table, the modified Fe-based functional material of Bacillus stearothermophilus prepared in this example is Cu2+The highest adsorption rate of the catalyst can reach 99.03 percent, and the catalyst can be used for treating Cd2+The highest adsorption rate of the catalyst can reach 98.34 percent.
Example 3
Taking 10.8g of ferric chloride hexahydrate and 320ml of ethylene glycol, magnetically stirring for 30min at room temperature, adding 16g of anhydrous sodium acetate, 40ml of diethylenetriamine and 2g of sodium dodecyl sulfate, stirring until the anhydrous sodium acetate, the diethylenetriamine and the sodium dodecyl sulfate are completely dissolved, transferring the mixture into a self-pressure reaction kettle containing a polytetrafluoroethylene lining, sealing the reaction kettle, reacting in a constant-temperature oven at 220 ℃ for 2h, taking out the reaction kettle, and naturally cooling to room temperature. Washing with deionized water and absolute ethyl alcohol, centrifuging at 4000r/min for 5min, taking the precipitate, and drying in a thermostat at 70 ℃ to obtain the iron-based functional material for later use.
Placing 2.5g of peptone and 2.5g of the prepared iron-based functional material in a conical flask, adding 250ml of water, placing in a high-pressure steam sterilization pot, sterilizing at 121 ℃ for 30min, inoculating 20 mu L of a saturated solution of Candida albicans, oscillating at constant temperature at the rotating speed of 170r/min, and oscillating at 37 ℃ for 4 days. Drying at 75 ℃, placing the dried precipitate in a crucible, heating to 550 ℃ at a heating rate of 5 ℃/min, and firing for 3 hours to obtain the modified iron-based functional material, wherein fig. 11 is a scanning electron microscope image of the modified iron-based functional material prepared in this embodiment: the modified iron-based functional material has uniform grain distribution, spherical shape and good overall appearance.
Taking 0.06g of candida albicans modified iron-based functional material, putting the material into an aqueous solution (prepared solution and not taken polluted water) containing heavy metal pollutants, adjusting the pH value to 5.38, oscillating the material in a constant temperature oscillator for 30min, and measuring the adsorbed Cu2+、Cd2+The capacity of (a) is shown in Table 3.
TABLE 3 Cu before and after adsorption of the modified Fe-based functional material prepared in example 32+、Cd2+In an amount of
As can be seen from the above table, the modified Fe-based functional material of Bacillus stearothermophilus prepared in this example is Cu2+The adsorption rate of the catalyst can reach 99.1 percent to Cd2+The highest adsorption rate of the catalyst can reach 98.46 percent.
Example 4
Respectively storing the modified iron-based functional materials prepared in the embodiments 1 to 3, dividing the modified iron-based functional materials prepared in each embodiment into 6 experimental groups, respectively taking 0.06g of the modified iron-based functional materials in each experimental group, putting the materials into an aqueous solution containing heavy metal pollutants, adjusting the pH value to 3 to 6, oscillating the materials in a constant temperature oscillator for 30min, and measuring the adsorbed Cu2+、Cd2+The concentrations of (A) and (B) are shown in Table 4.
Table 4, examples 1-3 prepare modified iron-based functional materials that adsorb Cu under different pH environments2+、Cd2+In an amount of
As can be seen from the above table, the optimal pH in example 1 is 5.38, the adsorption capacity of Cd ions in examples 2 and 3 increases with increasing pH to 5.38, and when the pH is greater than 5.38, the adsorption capacity decreases first and then increases, and it is appropriate to set the pH to 5.38. The adsorption capacity of the example 2 material to Cu ions in example 3 increases with increasing pH. In consideration of the above, it is preferable that the solutions in examples 1, 2 and 3 are weakly acidic, and therefore, it is preferable that the pH is 5.82.
Example 5
The modified iron-based functional materials prepared in examples 1 to 3 were stored separately, and the modified iron-based functional materials prepared in each example were divided into 8 experimentsIn each experimental group, 0.06g of each experimental group is respectively put into an aqueous solution containing heavy metal pollutants, the pH value is adjusted to 5.38, the solution is oscillated in a constant temperature oscillator for 3-50 min, and the Cu after adsorption is measured2+、Cd2+The concentrations of (A) and (B) are shown in Table 5.
Table 5, examples 1-3 modified iron-based functional materials adsorb Cu after different oscillation times2+、Cd2+In an amount of
As can be seen from the above table, in examples 1, 2 and 3, the control of Cd was carried out at 30min of oscillation time2+The adsorption effect is 1.36, 1.9 and 1.47 times of the lowest adsorption capacity; for Cu with 30min oscillation time in examples 1, 2 and 32+The adsorption effect is 1.01, 1.27 and 1.04 times of the lowest adsorption capacity. And (4) considering comprehensive factors, and the adsorption efficiency is highest when the adsorption time is oscillated for 30 min.
Example 6
Respectively storing the modified iron-based functional materials prepared in the embodiments 1-3, dividing the modified iron-based functional materials prepared in each embodiment into 5 experimental groups, respectively taking 0.01-0.07 g of the modified iron-based functional materials in each experimental group, putting the materials into an aqueous solution containing heavy metal pollutants, adjusting the pH value to 5.38, putting the materials into a constant temperature oscillator with the rotation speed of 170r/min at 25 ℃ for oscillation for 35min, measuring the adsorbed Cu, and measuring the adsorbed Cu2 +、Cd2+The calculated adsorption capacity is shown in table 6.
TABLE 6 Cu before and after adsorption of modified iron-based functional materials of different masses2+、Cd2+Concentration comparison of
As can be seen from the above table, the modified Fe-based functional materials prepared in examples 1-3 are used in an amount of 0.06g for Cu2+And Cd2+The adsorption effect of (2) is the best. In the embodiments 1, 2 and 3, the maximum adsorption efficiency of 0.06g on Cd ions is respectively 98.72%, 98.46% and 98.09%; in examples 1, 2 and 3, the maximum adsorption efficiency of the modified iron-based functional material to Cu ions is 98.61%, 99.10% and 99.03% respectively when the dosage is 0.06g, and the maximum adsorption efficiency is more than 98% when the dosage is 0.06 g.
Example 7
Taking 10.8g of ferric chloride hexahydrate and 320ml of ethylene glycol, magnetically stirring for 30min at room temperature, adding 16g of anhydrous sodium acetate, 40ml of diethylenetriamine and 2g of sodium dodecyl sulfate, stirring until the anhydrous sodium acetate, the diethylenetriamine and the sodium dodecyl sulfate are completely dissolved, transferring the mixture into a self-pressure reaction kettle containing a polytetrafluoroethylene lining, sealing, reacting in a constant-temperature oven at 185 ℃ for 1.8h, taking out, and naturally cooling to room temperature. Washing with deionized water and absolute ethyl alcohol, centrifuging at 4000r/min for 5min, taking the precipitate, and drying in a thermostat at 60 ℃ to obtain the iron-based functional material, wherein fig. 12 is a scanning electron microscope image of the iron-based functional material prepared in the embodiment: the modified iron-based functional material has uneven grain distribution and rough surface.
Placing 2.5g of peptone and 2.5g of the prepared iron-based functional material in a conical flask, adding 250ml of water, placing in a high-pressure steam sterilization pot, sterilizing at 121 ℃ for 30min, inoculating Aspergillus niger, wherein the bacterial dosage is 20 mu L of saturated solution, oscillating at constant temperature at the rotating speed of 170r/min, and oscillating at 37 ℃ for 6 days. Drying at 75 ℃, placing the dried precipitate in a crucible, heating to 550 ℃ at a heating rate of 5 ℃/min, and firing for 5 hours to obtain the modified iron-based functional material, wherein fig. 13 is a scanning electron microscope image of the aspergillus niger modified iron-based functional material prepared in the embodiment: the modified iron-based functional material has uneven grain distribution, curly shape and overall irregular shape.
Taking 0.06g of Aspergillus niger modified iron-based functional material, putting into an aqueous solution containing heavy metal pollutants, adjusting pH to 5.38, placing in a constant temperature oscillator with 25 ℃ and a rotating speed of 170r/min for oscillation for 35min, and measuring adsorbed Cu2+、Cd2+The concentrations of (A) are shown in Table 7.
TABLE 7 Cu before and after adsorption of the modified Fe-based functional material prepared in example 72+、Cd2+In an amount of
As can be seen from Table 7, 0.06g of the Aspergillus niger modified iron-based functional material prepared in example 7 was found to contain a low concentration of Cu2+(4.47、7.09mg/l)、Cd2+The adsorption rates in the aqueous solutions of (7.78, 14.41mg/l) are respectively more than 95%, and the aqueous solutions contain high concentration Cu2+(13.73、17.76mg/l)、Cd2+The adsorption rates in the aqueous solutions of (23.28, 31.11mg/l) respectively reach more than 40% and 80%, and the comprehensive factors are considered as follows: example 7 Aspergillus niger modified iron-based functional Material for heavy Metal Cu2+、Cd2+Has good adsorption effect.
Example 8
Taking 10.8g of ferric chloride hexahydrate and 320ml of ethylene glycol, magnetically stirring for 30min at room temperature, adding 16g of anhydrous sodium acetate, 40ml of diethylenetriamine and 2g of sodium dodecyl sulfate, stirring until the anhydrous sodium acetate, the diethylenetriamine and the sodium dodecyl sulfate are completely dissolved, transferring the mixture into a self-pressure reaction kettle containing a polytetrafluoroethylene lining, sealing, reacting in a constant-temperature oven at 185 ℃ for 2.2h, taking out, and naturally cooling to room temperature. Washing with deionized water and absolute ethyl alcohol, centrifuging at 4000r/min for 5min, taking the precipitate, and drying in a thermostat at 70 ℃ to obtain the iron-based functional material for later use.
Placing 2.5g of peptone and 2.5g of the prepared iron-based functional material in a conical flask, adding 250ml of water, placing in a high-pressure steam sterilization pot, sterilizing at 121 ℃ for 30min, inoculating 20 mu L of a saturated solution of Candida albicans, oscillating at constant temperature at the rotating speed of 170r/min, and oscillating at 37 ℃ for 6 days. Drying at 75 ℃, placing the dried precipitate in a crucible, heating to 550 ℃ at a heating rate of 5 ℃/min, and burning for 4h to obtain the modified iron-based functional material, wherein fig. 14 is a scanning electron microscope image of the candida albicans modified iron-based functional material prepared in the embodiment: the modified iron-based functional material has uneven grain distribution and overall irregular appearance.
Taking 0.06g of Candida albicans modified iron-based functional material, putting into an aqueous solution containing heavy metal pollutants, adjusting the pH to 5.38, placing in a constant temperature oscillator with the rotation speed of 170r/min at 25 ℃ for oscillation for 35min, and measuring the adsorbed Cu2+、Cd2+The concentrations of (A) are shown in Table 8.
TABLE 8 Cu before and after adsorption of the modified Fe-based functional material prepared in example 82+、Cd2+In an amount of
As can be seen from Table 8, 0.06g of the Candida albicans modified Fe-based functional material prepared in example 8 contained low concentration of Cu2+(4.47、7.09mg/l)、Cd2+The adsorption rate of the (7.78, 14.41mg/l) aqueous solution is more than 99 percent, and the aqueous solution contains high concentration Cu2+(13.73、17.76mg/l)、Cd2+The adsorption rates in the aqueous solutions of (23.28, 31.11mg/l) respectively reach more than 85% and 97%, and the comprehensive factors are considered as follows: example 8 the prepared Candida albicans modified iron-based functional material is heavy metal Cu2+、Cd2+Has good adsorption effect.
Example 9
Taking 10.8g of ferric chloride hexahydrate and 320ml of ethylene glycol, magnetically stirring for 30min at room temperature, adding 16g of anhydrous sodium acetate, 40ml of diethylenetriamine and 2g of sodium dodecyl sulfate, stirring until the anhydrous sodium acetate, the diethylenetriamine and the sodium dodecyl sulfate are completely dissolved, transferring the mixture into a self-pressure reaction kettle containing a polytetrafluoroethylene lining, sealing, reacting in a constant-temperature oven at 185 ℃ for 2h, taking out, and naturally cooling to room temperature. Washing with deionized water and absolute ethyl alcohol, centrifuging at 4000r/min for 5min, taking the precipitate, and drying in a thermostat at 65 ℃ to obtain the iron-based functional material.
Placing 2.5g of peptone and 2.5g of the iron-based functional material prepared above in a conical flask, adding 250ml of water, placing in a high pressure steam sterilization pot, sterilizing at 121 deg.C for 30min, inoculating Bacillus stearothermophilus with 20 μ L of saturated solution, oscillating at constant temperature of 170r/min, and oscillating at 37 deg.C for 6 days. Drying at 75 ℃, placing the dried precipitate in a crucible, heating to 550 ℃ at a heating rate of 5 ℃/min, and burning for 4h to obtain the modified iron-based functional material, wherein fig. 15 is a scanning electron microscope image of the bacillus stearothermophilus modified iron-based functional material prepared in the embodiment: the modified iron-based functional material has the advantages of uneven grain distribution, rough surface, slight curling at the edge and irregular overall appearance.
Taking 0.06g of Bacillus stearothermophilus modified iron-based functional material, putting into an aqueous solution containing heavy metal pollutants, adjusting pH to 5.38, placing in a constant temperature oscillator with 25 ℃ and the rotating speed of 170r/min for oscillation for 35min, measuring the adsorbed Cu2+、Cd2+The concentrations of (A) are shown in Table 9.
TABLE 9 Cu before and after adsorption of the modified Fe-based functional material prepared in example 92+、Cd2+In an amount of
As can be seen from Table 9, 0.06g of the modified iron-based functional material prepared in example 9 contained Cu at a low concentration2+(4.47、7.09mg/l)、Cd2+The adsorption rate of the (7.78, 14.41mg/l) aqueous solution is more than 97 percent, and the aqueous solution contains high concentration Cu2+(13.73、17.76mg/l)、Cd2+The adsorption rates in the aqueous solutions of (23.28, 31.11mg/l) respectively reach more than 83% and 97%, and the comprehensive factors are considered as follows: example 9 modified iron-based functional Material for heavy Metal Cu2+、Cd2+Has good adsorption effect.
Example 10
Taking 10.8g of ferric chloride hexahydrate and 320ml of ethylene glycol, magnetically stirring for 30min at room temperature, adding 16g of anhydrous sodium acetate, 40ml of diethylenetriamine and 2g of sodium dodecyl sulfate, stirring until the anhydrous sodium acetate, the diethylenetriamine and the sodium dodecyl sulfate are completely dissolved, transferring the mixture into a self-pressure reaction kettle containing a polytetrafluoroethylene lining, sealing, reacting in a constant-temperature oven at 185 ℃ for 2.2h, taking out, and naturally cooling to room temperature. Washing with deionized water and absolute ethyl alcohol, centrifuging at 4000r/min for 5min, taking the precipitate, and drying in a thermostat at 70 ℃ to obtain the iron-based functional material for later use.
Placing 2.5g of peptone and 2.5g of the prepared iron-based functional material in a conical flask, adding 250ml of water, placing in a high-pressure steam sterilization pot, sterilizing at 121 ℃ for 30min, and dividing into 4 experimental groups, wherein the first 3 groups are respectively inoculated with 20 mu L of saturated Aspergillus niger, Candida albicans and Bacillus stearothermophilus solution, and the 4 th group is a blank experimental group and is not inoculated. Shaking at constant temperature of 170r/min, and shaking at 37 deg.C for 6 days. Drying at 75 ℃, placing the dried precipitate in a crucible, heating to 550 ℃ at a heating rate of 5 ℃/min, and firing for 4h to obtain the modified iron-based functional material, wherein fig. 16 is a drawing showing that nitrogen gas of 3 modified iron-based functional materials and unmodified iron-based functional materials prepared in the embodiment is absorbed and removed: the adsorption-desorption isothermal curve of the material belongs to type IV, and the pore diameter distribution diagram is shown in figure 17: the pore size distribution curve indicates that there are sufficient mesopores and macropores; FIG. 18 is a graph of its pore volume: as can be seen from the figure, the specific surface area of the material in the four embodiments is 239.4m2/g、61.41m2/g、33.8m2G and 39.8m2XRD patterns of the samples show that etching of Aspergillus niger, Candida albicans and Bacillus thermophilus can change the lattice structure compared to four samples, and UN- α -Fe2O3representing untreated iron-based functional material, AN- α -Fe2O3representing an Aspergillus niger modified iron-based functional material, CA- α -Fe2O3representing a modified iron-based functional material of Candida albicans, BS- α -Fe2O3Represents a thermophilic bacillus modified iron-based functional material.
Respectively taking 0.06g of the prepared 3 groups of modified iron-based functional materials, putting the materials into an aqueous solution containing heavy metal pollutants, adjusting the pH value to 3-6, placing the materials in a constant temperature oscillator with the rotation speed of 170r/min at 25 ℃ for oscillation for 35min, and measuring the Cu after adsorption2+、Cd2+At pH, as shown in FIG. 20<At 5.38, Cd2+And Cu2+The adsorption capacity of (A) is gradually increased, and at pH 5.38, adsorption is carried outThe adsorption capacity reaches the maximum, and when the adsorption capacity exceeds 5.38, the adsorption capacity tends to decrease. Considering the comprehensive factors, the pH value is preferably 5.38.
Example 11
Taking 10.8g of ferric chloride hexahydrate and 320ml of ethylene glycol, magnetically stirring for 30min at room temperature, adding 16g of anhydrous sodium acetate, 40ml of diethylenetriamine and 2g of sodium dodecyl sulfate, stirring until the anhydrous sodium acetate, the diethylenetriamine and the sodium dodecyl sulfate are completely dissolved, transferring the mixture into a self-pressure reaction kettle containing a polytetrafluoroethylene lining, sealing, reacting in a constant-temperature oven at 185 ℃ for 2.2h, taking out, and naturally cooling to room temperature. Washing with deionized water and absolute ethyl alcohol, centrifuging at 4000r/min for 5min, taking the precipitate, and drying in a thermostat at 70 ℃ to obtain the iron-based functional material for later use.
Placing 2.5g of peptone and 2.5g of the prepared iron-based functional material in a conical flask, adding 250ml of water, placing in a high-pressure steam sterilization pot, sterilizing at 121 ℃ for 30min, then dividing into 3 experimental groups, respectively inoculating Aspergillus niger, Candida albicans and Bacillus stearothermophilus, oscillating at constant temperature at the rotating speed of 170r/min, and oscillating at 37 ℃ for 6 days. Drying at 75 ℃, placing the dried precipitate in a crucible, heating to 550 ℃ at the heating rate of 5 ℃/min, and burning for 4h to obtain the modified iron-based functional material.
Adding 0.01, 0.03, 0.05, 0.06 and 0.07g of the prepared 3 groups of modified iron-based functional materials into an aqueous solution containing heavy metal pollutants, adjusting the pH to 5.38, placing the solution in a constant temperature oscillator at 25 ℃ and the rotating speed of 170r/min for oscillation for 35min, and measuring the adsorbed Cu2+、Cd2+The concentration of (c). As a result, as shown in FIG. 21, the modified Fe-based functional material had good adsorption performance, and the rules of 3 groups were approximately the same, when the modified Fe-based functional material was added<0.05g, Cd with increasing amount of Cd2+And Cu2+The removal rate increases rapidly because as the amount of adsorbent increases, the total specific surface area and functional groups increase, and Cd2+And Cu2+The better the removal. When the adding amount is 0.05-0.06 g, Cd2+And Cu2+The removal rate tends to be stable and the adsorption balance is basically achieved.
Example 12
Taking 10.8g of ferric chloride hexahydrate and 320ml of ethylene glycol, magnetically stirring for 30min at room temperature, adding 16g of anhydrous sodium acetate, 40ml of diethylenetriamine and 2g of sodium dodecyl sulfate, stirring until the anhydrous sodium acetate, the diethylenetriamine and the sodium dodecyl sulfate are completely dissolved, transferring the mixture into a self-pressure reaction kettle containing a polytetrafluoroethylene lining, sealing, reacting in a constant-temperature oven at 185 ℃ for 2h, taking out, and naturally cooling to room temperature. Washing with deionized water and absolute ethyl alcohol, centrifuging at 4000r/min for 5min, taking the precipitate, and drying in a thermostat at 70 ℃ to obtain the iron-based functional material for later use.
Placing 2.5g of peptone and 2.5g of the prepared iron-based functional material in a conical flask, adding 250ml of water, placing in a high-pressure steam sterilization pot, sterilizing at 121 ℃ for 30min, then dividing into 3 experimental groups, respectively inoculating Aspergillus niger, Candida albicans and Bacillus stearothermophilus, oscillating at constant temperature at the rotating speed of 170r/min, and oscillating at 37 ℃ for 6 days. Drying at 75 ℃, placing the dried precipitate in a crucible, heating to 550 ℃ at the heating rate of 5 ℃/min, and burning for 3h to obtain the modified iron-based functional material.
Respectively taking 0.06 group of the prepared 3 modified iron-based functional materials, putting the materials into an aqueous solution containing heavy metal pollutants, adjusting the pH value to 5.38, putting the materials into a constant temperature oscillator with the rotation speed of 170r/min at 25 ℃ for 3, 5, 10, 15, 20, 30, 40 and 50min, and measuring the adsorbed Cu2+、Cd2+The concentration of (c). As shown in fig. 22, as the adsorption time increases, the adsorption rate gradually increases and then gradually levels. Before 10min, the change trend of the adsorption capacity along with time is large, the change range of the adsorption capacity is small between 10min and 30min, and after 30min, the curve is stable and basically reaches an equilibrium state.
Example 13
Taking 10.8g of ferric chloride hexahydrate and 320ml of ethylene glycol, magnetically stirring for 30min at room temperature, adding 16g of anhydrous sodium acetate, 40ml of diethylenetriamine and 2g of sodium dodecyl sulfate, stirring until the anhydrous sodium acetate, the diethylenetriamine and the sodium dodecyl sulfate are completely dissolved, transferring the mixture into a self-pressure reaction kettle containing a polytetrafluoroethylene lining, sealing, reacting in a constant-temperature oven at 185 ℃ for 2h, taking out, and naturally cooling to room temperature. Washing with deionized water and absolute ethyl alcohol, centrifuging at 4000r/min for 5min, taking the precipitate, and drying in a thermostat at 70 ℃ to obtain the iron-based functional material for later use.
Placing 2.5g of peptone and 2.5g of the prepared iron-based functional material in a conical flask, adding 250ml of water, placing in a high-pressure steam sterilization pot, sterilizing at 121 ℃ for 30min, and dividing into 4 experimental groups, wherein the first 3 experimental groups are respectively inoculated with 20 mu L of saturated Aspergillus niger, Candida albicans and Bacillus stearothermophilus solution, and the 4 th experimental group is a blank experimental group and is not inoculated with bacteria. Shaking at constant temperature of 170r/min, and shaking at 37 deg.C for 6 days. Drying at 75 ℃, placing the dried precipitate in a crucible, heating to 550 ℃ at the heating rate of 5 ℃/min, and burning for 3h to obtain the modified iron-based functional material.
Respectively taking 0.06 group of the prepared 3 modified iron-based functional materials and the iron-based functional materials which are not modified by bacteria, putting the materials into an aqueous solution containing heavy metal pollutants, adjusting the pH value to 5.38, placing the materials into a constant temperature oscillator with the rotation speed of 170r/min at 25 ℃ for oscillation for 30min, and then measuring the adsorbed Cu2+、Cd2+The concentration of (c). As a result, as shown in FIG. 23, when the amount of the adsorbent material was constant, Cd was added with the addition of Cd2+And Cu2+The adsorption capacity tends to be stable due to the increase of the concentration, and the adsorption capacity of the modified iron-based functional material is stronger than that of the unmodified iron-based functional material.
It should be understood that the detailed description and specific examples, while indicating embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
Claims (7)
1. The application of the modified iron-based functional material in heavy metal pollution remediation is characterized in that the application is specifically to adsorption of Cu in heavy metal polluted water2+And Cd2+(ii) a The modified iron-based functional material is prepared by taking ferric chloride hexahydrate, ethylene glycol, anhydrous sodium acetate, diethylenetriamine and sodium dodecyl sulfate as raw materials, reacting to prepare the iron-based functional material, and inoculating microorganisms.
2. According toUse of the modified iron-based functional material according to claim 1 for heavy metal pollution remediation, wherein the modified iron-based functional material adsorbs Cu2+And Cd2+The method comprises the following specific steps: and (3) placing the modified iron-based functional material in an aqueous solution containing heavy pollutants, adjusting the pH to 3-6, and placing the modified iron-based functional material in a constant-temperature oscillator at the temperature of 25 ℃ and the rotating speed of 170 ℃ for oscillation for 3-50 min.
3. The use of the modified iron-based functional material in heavy metal pollution remediation according to claim 2, wherein the pH is 5.38 and the time of oscillation is 30 min.
4. The use of the modified iron-based functional material in heavy metal pollution remediation according to claim 1, wherein the modified iron-based functional material is prepared by the following steps: putting ferric chloride hexahydrate in a beaker, adding ethylene glycol, stirring for 30-40 min, adding anhydrous sodium acetate, diethylenetriamine and sodium dodecyl sulfate, stirring until the anhydrous sodium acetate, diethylenetriamine and sodium dodecyl sulfate are completely dissolved, transferring the mixture into a self-pressure reaction kettle with a polytetrafluoroethylene lining, sealing, reacting at the constant temperature of 180-220 ℃ for 1.8-2.2 h, cooling to room temperature, washing, centrifuging and drying to obtain the iron-based functional material; mixing peptone and an iron-based functional material, adding water for sterilization, inoculating microorganisms, oscillating at constant temperature, taking precipitate, drying and firing at high temperature to obtain the modified iron-based functional material.
5. The application of the modified iron-based functional material in heavy metal pollution remediation, according to claim 4, wherein the mass ratio of the sodium dodecyl sulfate to the anhydrous sodium acetate to the ferric chloride hexahydrate is 5: 40: 17, the ethylene glycol: the volume ratio of diethylenetriamine is 8-10: 1.
6. the use of the modified iron-based functional material according to claim 4 for heavy metal contamination remediation, wherein the microorganism is Aspergillus niger, Candida albicans or Bacillus stearothermophilus.
7. The application of the modified iron-based functional material in heavy metal pollution remediation according to claim 6, wherein the ratio of the iron-based functional material to the saturated solution of microorganisms is 125 g: 1 mL.
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| JING QIAN ET.AL: "Preparation of NH2-Functionalized Fe2O3 and Its Chitosan Composites for the Removal of Heavy Metal Ions", 《SUSTAINABLITY》 * |
| 闫萌萌等: "微生物改性钢渣去除废水中砷(II)的性能研究", 《武汉理工大学学报》 * |
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Application publication date: 20200519 |