CN114351290B - Preparation method and application of lanthanum-zirconium-iron composite oxide porous nanofiber - Google Patents
Preparation method and application of lanthanum-zirconium-iron composite oxide porous nanofiber Download PDFInfo
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 46
- 239000011737 fluorine Substances 0.000 claims description 26
- 229910052731 fluorine Inorganic materials 0.000 claims description 26
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000003463 adsorbent Substances 0.000 claims description 6
- 230000008929 regeneration Effects 0.000 claims description 5
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- 230000005389 magnetism Effects 0.000 claims 1
- 239000002516 radical scavenger Substances 0.000 claims 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 6
- -1 fluoride ions Chemical class 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 230000002349 favourable effect Effects 0.000 abstract description 2
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- 238000010438 heat treatment Methods 0.000 description 15
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
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- 238000004438 BET method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical class [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
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- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
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Abstract
The invention provides a preparation method and application of lanthanum-zirconium-iron composite oxide porous nanofiber. The preparation method comprises the following steps: (1) Mixing polyacrylonitrile, nanoscale ferroferric oxide, lanthanum nitrate hexahydrate and zirconium chloride tetrahydrate with an organic solvent to obtain a precursor spinning solution; (2) Using electrostatic spinning equipment to enable the precursor spinning solution to carry out electrostatic spinning at 100-150kV/m to obtain precursor nanofibers; (3) And drying the precursor nanofiber and calcining at 450-750 ℃ to obtain the lanthanum-zirconium-iron composite oxide porous nanofiber. The preparation method is simple and low in cost; the prepared lanthanum-zirconium-iron composite oxide porous nanofiber material has a relatively high specific surface area, is favorable for adsorbing fluoride ions, and can be widely applied to treatment of industrial fluoride-containing wastewater.
Description
Technical Field
The invention relates to a porous nanofiber material, and belongs to the technical field of adsorption materials.
Background
The reasons for fluoride pollution of ground and surface water are mainly natural and human activities, such as leaching of fluorine-containing minerals through rain water due to erosion, resulting in water pollution. In addition, the discharge of industrial wastewater from semiconductor manufacturing, electroplating, aluminum and steel production, metal finishing, and the like can also cause fluoride pollution in the water body. The drinking of water with fluoride exceeding standard for a long time can cause serious harm to human health, so the treatment of fluorine-containing wastewater is an urgent problem to be solved in current water environment protection.
Among the many fluorine removal techniques, the adsorption method has advantages of low cost and simple operation, and is considered as the most promising one. Commonly used fluorine scavengers are zeolite, activated alumina, activated carbon, bone charcoal, activated magnesia and the like. However, the low adsorption rate and low adsorption capacity of the fluorine removing agent make the fluorine removing agent limited in practical application. In recent years, trivalent and tetravalent metal (Fe, al, la, mn and Zr) oxides and hydroxides (also referred to as hydrous oxides or oxyhydroxides) have been used for removing pollutants such as anions in wastewater, and they have strong affinity for anionic pollutants in wastewater, strong adsorption capacity and high adsorption speed. Zirconia (ZrO) 2 ) Is a chemically inert inorganic metal oxide with high stability to acids, alkalis, oxidizing agents and reducing agents. Zirconium ions have been used to remove fluoride and arsenic from aqueous solutions. The fluorine removal capacity of the nanoscale particulate zirconia-iron oxide (GZI) prepared by extrusion by Zhang et al was 9.8mg/g [ Water Research, 2011, 45:3571-3578]. ZrO prepared by one-step calcination method by Mei et al 2 the/BC defluorination capacity is 11.04mg/g [ Applied Surface Science, 2020, 509, 144685 ]]. In recent years, a method of mixing a rare earth metal, which is expensive, with an inexpensive metal or supporting the rare earth metal on a support material has been employed to prepare a new adsorbent, and the amount of the expensive rare earth metal is reduced to thereby reduce the cost while maintaining a high fluorine adsorption capacity. Wang et al synthesized a flaky Mg-Fe-La trimetallic composite material with excellent defluorination performance by a coprecipitation method, and the maximum adsorption capacity112.17mg/g [ Chemical Engineering Journal, 2015, 264:506-513)]。
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method and application of lanthanum-zirconium-iron composite oxide porous nanofiber. The preparation method of the lanthanum-zirconium-iron composite oxide porous nanofiber is simple, has high fluorine removal efficiency and can be reused, and the defects that the existing powder fluorine removal agent is not easy to recycle and the like are overcome.
The invention provides a preparation method of lanthanum-zirconium-iron composite oxide porous nanofiber, which comprises the following steps:
(1) Polyacrylonitrile (PAN), nanoscale ferroferric oxide (Fe) 3 O 4 ) Lanthanum nitrate hexahydrate (La (NO) 3 ) 3 ·6H 2 O), zirconium chloride tetrahydrate (ZrCl) 4 ·4H 2 O) mixing with an organic solvent to obtain a precursor spinning solution;
(2) Using electrostatic spinning equipment to enable the precursor spinning solution to carry out electrostatic spinning at 100-150kV/m to obtain precursor nanofibers;
(3) And drying the precursor nanofiber and calcining at 450-750 ℃ to obtain the lanthanum-zirconium-iron composite oxide porous nanofiber.
Preferably, the organic solvent in the step (1) is N, N-Dimethylformamide (DMF).
According to a preferred scheme, the dosage of polyacrylonitrile in the step (1) is 1.5-1.8 g, the dosage of nanoscale ferroferric oxide is 70-80 mg, the dosage of lanthanum nitrate hexahydrate is 0.7-0.75 g, the dosage of zirconium chloride tetrahydrate is 0.38-0.40 g, and the dosage of N, N-dimethylformamide is 8-12 mL.
Preferably, the precursor spinning solution supply rate of the electrostatic spinning in the step (2) is 1mL/h, and the receiving distance is 15cm.
Preferably, the precursor nanofiber in the step (3) is placed in a vacuum oven at 80 ℃ to be dried for 12 hours.
In the step (3), calcination is preferably performed in an air atmosphere tube furnace, and the calcination time is 1-3 hours.
The lanthanum-zirconium-iron composite oxide porous nanofiber obtained by the preparation method is of a porous nanofiber structure, the diameter of the nanofiber is 924+/-87 nm, and the specific surface area can reach 66.48m 2 Per gram, the pore volume can reach 0.134cm 3 The average pore diameter can reach 3.82nm.
The lanthanum zirconium iron composite oxide porous nanofiber obtained by the preparation method can be used as a defluorination adsorbent.
Compared with the prior art, the invention has the following beneficial effects:
1. the prepared lanthanum-zirconium-iron composite oxide porous nanofiber has high selectivity on fluoride ions, and other coexisting anions in water have small influence on fluoride ions;
2. the prepared lanthanum-zirconium-iron composite oxide porous nanofiber exists in a fiber membrane form, is stable and magnetic, can be separated by adopting a common external magnetic field, and is favorable for recycling for multiple times;
3. the prepared lanthanum-zirconium-iron composite oxide porous nanofiber has the fluorine removal capacity as high as 43.99mg/g and excellent adsorption performance, and can be regenerated through alkali liquid desorption;
4. the diameter of the prepared lanthanum-zirconium-iron composite oxide porous nanofiber can reach 924+/-87 nm, and the specific surface area can reach 66.48m 2 /g, pore size distribution can reach 3.82 nm;
5. the lanthanum-zirconium-iron composite oxide porous nanofiber has the advantages of low cost, simple preparation process, environment friendliness, reproducibility, magnetic separation, no secondary pollution and high application value.
Drawings
Fig. 1 is an SEM image of a lanthanum zirconium iron composite oxide porous nanofiber prepared in example 1 of the present invention.
FIG. 2 is a schematic diagram of N of a porous nanofiber of lanthanum zirconium iron composite oxide prepared in example 1 of the present invention 2 Adsorption-desorption graph.
Fig. 3 is a graph showing the adsorption effect of the lanthanum-zirconium-iron composite oxide porous nanofiber fluorine removing agent prepared in example 1 in water samples with different pH values.
Detailed Description
The present invention will be described in detail with reference to the drawings and the specific embodiments, but the scope of the present invention is not limited to the following.
The basic principle of the invention is as follows:
1. nano-scale Fe 3 O 4 Zirconium chloride tetrahydrate, lanthanum nitrate hexahydrate and polyacrylonitrile are respectively dispersed or dissolved in N, N-dimethylformamide, and the above-mentioned solutions are blended so as to obtain La (NO) 3 ) 3 /ZrCl 4 /Fe 3 O 4 PAN/DMF spinning solution, la (NO 3 ) 3 /ZrCl 4 /Fe 3 O 4 PAN nanofibers;
2. la (NO) 3 ) 3 /ZrCl 4 /Fe 3 O 4 PAN nanofibers are heat treated in air to give PAN, la (NO 3 ) 3 And ZrCl 4 Completely decomposing to obtain the lanthanum-zirconium-iron composite oxide with porous fiber morphology.
The diameter and morphology of the lanthanum zirconium iron composite oxide porous nanofiber can be controlled by conditions such as polyacrylonitrile solution concentration, electric field strength, heat treatment time and heat treatment temperature. The lanthanum zirconium content ratio can be controlled by adjusting the concentrations of lanthanum nitrate hexahydrate and zirconium chloride tetrahydrate. The lanthanum-zirconium-iron composite oxide porous nanofiber is very suitable for industrial fluorine-containing wastewater treatment, and the treated wastewater meets the national comprehensive wastewater discharge standard.
In a specific operation, the preparation method of the lanthanum zirconium iron composite oxide porous nanofiber can comprise the following steps:
(1) Adding polyacrylonitrile into N, N-dimethylformamide DMF, magnetically stirring uniformly, and dissolving to obtain a solution A; the nano-scale Fe 3 O 4 Ultrasonic dispersion is carried out in a small amount of DMF to obtain solution B; adding lanthanum nitrate hexahydrate and zirconium chloride tetrahydrate into DMF, and magnetically stirring uniformly to obtain a solution C; uniformly mixing the three solutions, and blending to obtain a precursor spinning solution;
(2) Injecting the precursor spinning solution into a plastic injector with a needle point, then placing the plastic injector into high-voltage electrostatic spinning equipment, wherein the supply speed is 1mL/h, the receiving distance is 15cm, and obtaining precursor nanofibers through electrostatic spinning at 100-150 kV/m;
(3) Placing the precursor fiber in a vacuum oven at 80 ℃ for drying for 12 hours; and (3) placing the dried precursor nanofiber in an air atmosphere tube furnace, and calcining for a certain time at a certain temperature to obtain the lanthanum-zirconium-iron composite oxide defluorination porous nanofiber.
Several exemplary embodiments are listed below.
Example 1
The preparation method of the lanthanum zirconium iron composite oxide porous nanofiber specifically comprises the following steps:
1.8g of polyacrylonitrile is dissolved in 8mL of N, N-dimethylformamide, and the solution A is obtained after magnetic stirring for 8 hours to completely dissolve the polyacrylonitrile;
0.0753g of Fe 3 O 4 Particles are dispersed in 2mL of N, N-dimethylformamide by ultrasonic wave to obtain a solution B;
0.708g of lanthanum nitrate hexahydrate and 0.3800g of zirconium chloride tetrahydrate were dissolved in 2mL of N, N-dimethylformamide to obtain a solution C;
uniformly mixing the solution A, the solution B and the solution C to obtain a spinning solution; filling the spinning solution into a plastic injector with a needle point, then placing the plastic injector into high-voltage electrostatic spinning equipment, enabling the supply speed to be 0.8mL/min, performing electrostatic spinning at 100-150kV/m to obtain precursor nanofibers, and then placing the precursor nanofibers into a vacuum oven at 80 ℃ for drying for 12 hours;
placing the dried precursor nanofiber in an air atmosphere tube furnace, heating from room temperature to 220 ℃, keeping the heating rate at 1 ℃/min at 220 ℃ for 3 hours, heating from 220 ℃ to 500 ℃ at the heating rate of 3 ℃/min, and keeping the temperature at 500 ℃ for 2 hours to obtain the lanthanum-zirconium-iron composite oxide porous nanofiber, wherein the heating rate is 1 ℃/min, and the nanoscale Fe is the nano-grade Fe 3 O 4 The particles are uniformly dispersed in the porous nanofibers.
As shown in FIG. 1, the scanning electron microscope of the lanthanum-zirconium-iron composite oxide porous nanofiber prepared in the embodiment has a porous structure with a diameter of 924+ -87nm. FIG. 2 is N of lanthanum zirconium iron composite oxide porous nanofiber 2 Adsorption-desorption curves. The comparative area of the lanthanum-zirconium-iron composite oxide porous nanofiber measured by adopting the BET method is 66.48m 2 And/g, the pore size distribution is 3.82 and nm, which is beneficial to improving the fluorine removal capability.
Example 2
The preparation method of the lanthanum zirconium iron composite oxide porous nanofiber specifically comprises the following steps:
1.8g of polyacrylonitrile is dissolved in 8mL of N, N-dimethylformamide, and the solution A is obtained after magnetic stirring for 8 hours to completely dissolve the polyacrylonitrile;
0.0753g of Fe 3 O 4 Particles are dispersed in 2mL of N, N-dimethylformamide by ultrasonic wave to obtain a solution B;
0.708g of lanthanum nitrate hexahydrate and 0.3800g of zirconium chloride tetrahydrate were dissolved in 2mL of N, N-dimethylformamide to obtain a solution C;
uniformly mixing the solution A, the solution B and the solution C to obtain a spinning solution; filling the spinning solution into a plastic injector with a needle point, then placing the plastic injector into high-voltage electrostatic spinning equipment, enabling the supply speed to be 0.8mL/min, performing electrostatic spinning at 100-150kV/m to obtain precursor nanofibers, and then placing the precursor nanofibers into a vacuum oven at 80 ℃ for drying for 12 hours;
and (3) placing the dried precursor nanofiber in an air atmosphere tube furnace, heating from room temperature to 230 ℃, keeping the heating rate at 1 ℃/min for 3 hours at 230 ℃, heating from 230 ℃ to 600 ℃ at the heating rate of 5 ℃/min, and keeping the temperature at 600 ℃ for 2 hours to obtain the lanthanum-zirconium-iron composite oxide porous nanofiber.
The lanthanum zirconium iron composite oxide porous nanofiber prepared in the embodiment has a porous structure and the diameter is 825+/-90 nm. The comparative area was 46.05m by BET method 2 And/g, the pore size distribution is 3.82 and nm, which is beneficial to improving the fluorine removal capability.
Example 3
The preparation method of the lanthanum zirconium iron composite oxide porous nanofiber specifically comprises the following steps:
1.8g of polyacrylonitrile is dissolved in 8mL of N, N-dimethylformamide, and the solution A is obtained after magnetic stirring for 8 hours to completely dissolve the polyacrylonitrile;
0.0753g of Fe 3 O 4 Particles are dispersed in 2mL of N, N-dimethylformamide by ultrasonic wave to obtain a solution B;
0.708g of lanthanum nitrate hexahydrate and 0.3800g of zirconium chloride tetrahydrate were dissolved in 2mL of N, N-dimethylformamide to obtain a solution C;
uniformly mixing the solution A, the solution B and the solution C to obtain a spinning solution; filling the spinning solution into a plastic injector with a needle point, then placing the plastic injector into high-voltage electrostatic spinning equipment, enabling the supply speed to be 0.8mL/min, performing electrostatic spinning at 100-150kV/m to obtain precursor nanofibers, and then placing the precursor nanofibers into a vacuum oven at 80 ℃ for drying for 12 hours;
and (3) placing the dried precursor nanofiber in an air atmosphere tube furnace, heating from room temperature to 230 ℃, keeping the heating rate at 1 ℃/min for 3 hours at 230 ℃, heating from 230 ℃ to 700 ℃ at the heating rate of 5 ℃/min, and keeping the temperature at 700 ℃ for 1 hour to obtain the lanthanum-zirconium-iron composite oxide porous nanofiber.
The lanthanum zirconium iron composite oxide porous nanofiber prepared in the embodiment has a porous structure and the diameter is 780+/-74 nm. The comparative area was 36.71. 36.71 m by BET method 2 And/g, the diameter distribution is 3.82 and nm, which is beneficial to improving the fluorine removal capability.
Example 4
The lanthanum zirconium iron composite oxide porous nanofiber prepared in the examples 1-3 is used as a defluorination adsorbent to verify the defluorination effect, and the specific operation is as follows: 0.01g of lanthanum zirconium iron composite oxide porous nanofiber defluorinating agent is added into 50mL of fluorine-containing solution with the mass concentration of 10mg/L, the pH value is 3, the mixture is oscillated for 12 hours in a constant temperature oscillator at 35 ℃, the mixture is stood and filtered, the concentration of fluorine ions in the filtrate is measured, and the measurement result of the adsorption quantity is shown in table 1. After adsorbing fluorine, the fluorine removing agent adopts 0.1mol/L NaOH solution for desorption regeneration, magnetic separation, washing and drying, and is recorded as 1-time recycling regeneration, and after the adsorbent is repeatedly recycled for 5 times, the regeneration efficiency is maintained to be above 80%.
Table 1 adsorption amount of porous nanofiber of lanthanum-zirconium-iron composite oxide prepared in examples 1 to 3 to fluorine solution
| Defluorination adsorbent | Initial fluoride ion concentration (mg.L) -1 ） | Adsorption quantity (mg.g) -1 ） |
| Example 1 | 10 | 43.99 |
| Example 2 | 10 | 42.02 |
| Example 3 | 10 | 42.87 |
As shown in Table 1, the lanthanum-zirconium-iron composite oxide porous nanofiber prepared by the invention has excellent defluorination effect as a defluorination material.
According to the embodiment, the lanthanum-zirconium-iron composite oxide porous nanofiber prepared by the method has a porous nanofiber structure, and is high in specific surface area, good in fluorine removal performance and good in recycling performance.
The foregoing is only a preferred embodiment of the present invention. It is to be understood that the invention is not limited to the particular embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the claims without affecting the spirit of the invention.
Claims (4)
1. The application of lanthanum zirconium iron composite oxide porous nanofiber as a fluorine removing agent is characterized in that: the preparation method of the lanthanum zirconium iron composite oxide porous nanofiber comprises the following steps:
(1) Mixing polyacrylonitrile, nanoscale ferroferric oxide, lanthanum nitrate hexahydrate, zirconium chloride tetrahydrate and an organic solvent N, N-dimethylformamide to obtain a precursor spinning solution;
(2) Using electrostatic spinning equipment to enable the precursor spinning solution to carry out electrostatic spinning at 100-150kV/m to obtain precursor nanofibers;
(3) Drying the precursor nanofiber and calcining at 450-750 ℃ to obtain the lanthanum-zirconium-iron composite oxide porous nanofiber;
in the step (1), the dosage of polyacrylonitrile is 1.5-1.8 g, the dosage of nanoscale ferroferric oxide is 70-80 mg, the dosage of lanthanum nitrate hexahydrate is 0.7-0.75 g, the dosage of zirconium chloride tetrahydrate is 0.38-0.40 g, and the dosage of N, N-dimethylformamide is 8-12 mL;
the lanthanum zirconium iron composite oxide porous nanofiber has magnetism; the lanthanum-zirconium-iron composite oxide porous nanofiber is used as a fluorine removing agent to adsorb fluorine, then is desorbed and regenerated by adopting a 0.1mol/L NaOH solution, is magnetically separated, is washed and dried, and is recorded as 1-time recycling regeneration, and the regeneration efficiency is maintained to be above 80% after the adsorbent is repeatedly recycled for 5 times.
2. The use of lanthanum zirconium iron composite oxide porous nanofiber as claimed in claim 1 as a fluorine scavenger, characterized in that: in the step (2), the supply rate of the precursor spinning solution for electrostatic spinning is 1mL/h, and the receiving distance is 15cm.
3. Use of lanthanum zirconium iron composite oxide porous nanofiber according to claim 1 or 2 as defluorinating agent, characterized in that: in the step (3), the precursor nanofiber is placed in a vacuum oven at 80 ℃ and dried for 12 hours.
4. Use of lanthanum zirconium iron composite oxide porous nanofiber according to claim 1 or 2 as defluorinating agent, characterized in that: and (3) calcining in the step (3) is performed in an air atmosphere tube furnace, and the calcining time is 1-3 h.
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