CN114749139A - Amorphous nano zero-valent iron, preparation method thereof and application of amorphous nano zero-valent iron in removing antimony in water body - Google Patents
Amorphous nano zero-valent iron, preparation method thereof and application of amorphous nano zero-valent iron in removing antimony in water body Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 65
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- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 229910052787 antimony Inorganic materials 0.000 title abstract description 8
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000011282 treatment Methods 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
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- 150000002505 iron Chemical class 0.000 claims abstract description 11
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- 239000000243 solution Substances 0.000 claims description 44
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- 238000003756 stirring Methods 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 11
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 claims description 9
- 230000010355 oscillation Effects 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
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- 230000009467 reduction Effects 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000004698 Polyethylene Substances 0.000 description 13
- 239000011521 glass Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
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- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 11
- 239000002351 wastewater Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
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- 238000005516 engineering process Methods 0.000 description 3
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- 238000012986 modification Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
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- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
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- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- TXTQARDVRPFFHL-UHFFFAOYSA-N [Sb].[H][H] Chemical compound [Sb].[H][H] TXTQARDVRPFFHL-UHFFFAOYSA-N 0.000 description 1
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
The invention discloses amorphous nano zero-valent iron, a preparation method thereof and application of the amorphous nano zero-valent iron in removing antimony in a water body. The invention uses a liquid phase reduction method, introduces ethylenediamine into iron salt as an iron source, reduces the iron source by adding a reducing agent, and centrifugally collects the iron source after the reaction is finished to obtain A-nZVI. Compared with the traditional nano iron, the prepared A-nZVI has high specific surface area, more pollutant adsorption sites, high-efficiency removal effect and good selectivity on Sb (III), and is more stable in removal; can be used as an effective water body Sb (III) pollution adsorbent to be applied to the field of water body heavy metal pollution treatment.
Description
Technical Field
The invention belongs to the field of nano materials and environmental remediation, and particularly relates to amorphous nano zero-valent iron (A-nZVI), a preparation method thereof and application thereof in removing antimony (III) in a water body.
Background
In recent years, antimony pollution in water has attracted global attention. The concentration of antimony in natural water is usually less than 1. mu.g/L, but the concentration of antimony dissolved in surface water and ground water around mining and smelting plants ranges up to 4.58-29.4 mg/L. Antimony in aqueous environments exists as sb (iii) under reducing conditions and sb (v) under oxidizing conditions. Sb (III) is ten times as toxic as Sb (V), and has been classified as a priority pollutant by the World Health Organization (WHO) due to its high toxicity and carcinogenicity, and the WHO stipulates that the maximum pollutant level of antimony in drinking water is 6 mug/L, while China requires 5 mug/L.
At present, the treatments of Sb (III) mainly comprise a chemical precipitation method, an adsorption method, a membrane technology, an ion exchange resin, an electrochemical method and the like. When the initial concentration of Sb (III) is high, the precipitation rule cannot meet the strict regulation of the Sb in effluent, but in the seawater desalination process, the Sb removal by membrane filtration does not have good selectivity, and the electrochemical method can achieve ideal removal efficiency, but the high cost and excessive energy consumption limit the wide application of the method; the adsorption method is considered as one of the best treatment technologies for removing Sb in water at present due to the advantages of low cost, simple design, wide applicable concentration range and the like.
The zero-valent iron material is cheap and easy to obtain and has the advantage of environmental friendliness, but the removal capacity is low due to the large particle size and the inherent passivation layer limits the reactivity of the zero-valent iron material, so that the application range is limited. With the development of nanotechnology, nanoscale zero-valent iron (nZVI) has been widely used for the treatment of halogenated organic substances and heavy metals due to its high specific surface area and high reactivity, and has also been used for the treatment of sb (iii). However, the adsorption of nano zero-valent iron (nZVI) to sb (iii) is unstable, and under an acidic condition, the adsorbed sb (iii) is easily released from particles due to corrosion of nZVI and dissolution of iron oxide, which affects the removal effect and stability, so that how to perform crystal face regulation on the sb (iii) to improve the reactivity and the stability is urgently needed to be solved.
Disclosure of Invention
In order to solve the defects of Sb (III) polluted water bodies in the prior art, the invention mainly aims to provide a preparation method of amorphous nano zero-valent iron (A-nZVI).
The invention also aims to provide the amorphous nano zero-valent iron (A-nZVI) prepared by the method.
The invention further aims to provide application of the amorphous nano zero-valent iron (A-nZVI) in removing trivalent antimony in a water body.
According to the method, the trivalent antimony polluted water body is treated by adopting the amorphous nano zero-valent iron nano material, the heavy metal Sb (III) is treated by utilizing the amorphous nano zero-valent iron (A-nZVI), and the Sb (III) is efficiently removed through adsorption and oxidation, so that the mobility of the Sb (III) in the water body is greatly reduced, and the aim of repairing underground water and surface water of a polluted site is fulfilled. The method has the advantages of low cost and simple process, and the prepared material has high reactivity, good stability and strong selectivity, and is suitable for industrial production.
The purpose of the invention is realized by the following technical scheme:
a preparation method of amorphous nano zero-valent iron (A-nZVI) comprises the following steps:
under the protection of nitrogen or inert gas, adding Ethylenediamine (EDA) into the ferric salt solution, uniformly mixing, adding a reducing agent, and stirring for reaction to obtain the amorphous nano zero-valent iron (A-nZVI).
Preferably, the molar ratio of iron in the ethylenediamine and the iron salt is 2.5: 1-3.5: 1.
preferably, the iron salt in the iron salt solution is ferric chloride.
Preferably, the concentration of the iron salt solution is 0.045-0.055 mol/L, and the solvent is water.
Preferably, the reducing agent is NaBH4。
Preferably, the molar ratio of the reducing agent to iron in the iron salt is 25: 9-50: 9.
preferably, the reducing agent is added in the form of reducing agent solution with the concentration of 0.2-0.3 mol/L, and the solvent is water.
Preferably, the reducing agent is added in a dropwise manner, and the dropwise adding speed is 40-50 mL/min.
More preferably, after the reducing agent is dropwise added, the stirring reaction time is 10-20 minutes, and the stirring rotation speed is 550-600 r/min.
Preferably, after the stirring reaction is finished, collecting the precipitate, and alternately washing with deionized water and absolute ethyl alcohol to obtain the amorphous nano zero-valent iron (A-nZVI).
The particle size of the amorphous nano zero-valent iron (A-nZVI) obtained by the invention is about 10 nm.
The amorphous nano zero-valent iron (A-nZVI) prepared by the method.
The application of the amorphous nano zero-valent iron (A-nZVI) in removing trivalent antimony in a water body.
Preferably, the application is: adding amorphous nano zero-valent iron (A-nZVI) into a water body containing Sb (III) and having the pH value of 3-11, and removing by shaking, wherein the amorphous nano zero-valent iron is used as an Sb (III) removing adsorbent.
More preferably, the pH is 5 to 11.
More preferably, the oscillation is constant-temperature oscillation, the temperature is 25 +/-0.2 ℃, the oscillation reaction time is not less than 4 hours, and the oscillation speed is 200-250 r/min.
More preferably, the concentration of Sb (III) in the water body is 50-250 mg/L; more preferably 50 to 150 mg/L.
More preferably, the mass volume ratio of the amorphous nanoscale zero-valent iron to the water body is 0.02-0.05 g: 100-500 mL.
More preferably, the shaking removal is performed in a closed reaction bottle, and the oxygen removal treatment is performed by introducing nitrogen or inert gas before the amorphous nano zero-valent iron is added.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the A-nZVI prepared by the invention is a modification technology of nano iron, and compared with a common nano iron material, the A-nZVI has high specific surface area and more active sites, and the efficiency of treating Sb (III) pollution in water is increased. The A-nZVI prepared by the invention improves the oxidation resistance, stability and selectivity of the nano iron particles, has higher removing capability on Sb (III) environmental pollutants, and is suitable to be used as an adsorbent in the field of water environment heavy metal pollution treatment.
Drawings
FIG. 1 is an X-ray powder diffractometer (XRD) analysis pattern of ordinary zero-valent nano-iron (nZVI) in comparative example 1 and A-nZVI in example 1.
FIG. 2 is a Scanning Electron Microscope (SEM) analysis of A-nZVI in example 1.
FIG. 3 is a graph comparing the removal rates of 0.5g/L of nZVI and A-nZVI for Sb (III) in example 2.
FIG. 4 is a graph showing the effect of 0.2g/L A-nZVI on the degradation of Sb (III) at different concentrations in examples 3-7.
FIG. 5 is a graph showing the effect of 0.2g/L A-nZVI on the degradation of Sb (III) in different pH environments in examples 8-12.
FIG. 6 is the removal capacity of example 13 for five cycles of 0.2g/L A-nZVI.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
The examples of the present invention, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.
The water used in comparative example 1 and example 1 was deionized water.
Comparative example 1
Preparing nZVI by liquid phase reduction method, adding 400mL NaBH4(0.25mol/L) aqueous solution was added dropwise to an equal volume of FeCl at a flow rate of 45mL/min 3(0.045mol/L) water solution, stirring the solution at a rotating speed of 600r/min by using an electric stirring rod, continuously stirring for 15min after the dripping is finished, fully reacting to release hydrogen, centrifuging and collecting to obtain precipitate, and adding deionized water and anhydrous sodium chlorideAnd washing with water and ethanol alternately for 2 times to obtain nZVI.
Example 1
At N260mL of an aqueous solution of ethylenediamine (EDA,0.9mol/L) was added to 340mL of FeCl under an atmosphere3Stirring and fully mixing (0.053mol/L) aqueous solution for 5min at 360r/min to finally obtain FeCl3And EDA as an iron source, 400mL of NaBH4And (0.25mol/L) aqueous solution is dropwise added into the mixed solution with the same volume, an electric stirring rod is used for stirring the solution at the rotating speed of 600r/min, stirring is continued for 15min after dropwise addition is finished, the solution is fully reacted to release hydrogen, then, the solution is centrifugally collected to obtain precipitate, and the precipitate is alternately washed for 2 times by deionized water and absolute ethyl alcohol to obtain the A-nZVI. The washed materials are sealed by absolute ethyl alcohol and stored in a refrigerator at 4 ℃ for later use.
Example 2
A150-ml glass bottle with a polyethylene screw cap was used as a reactor, 100ml of 100mg/L aqueous Sb (III) solution (initial pH 4.8-5.0) was introduced thereinto, and 8min of N was passed therethrough2The dissolved oxygen was removed, and then 0.05g of nZVI or A-nZVI was added and the reaction was carried out at normal temperature (25. + -. 0.2 ℃ C.) in a shaker at 200 r/min. 1.0mL of the mixture was taken from the reaction flask at a preset time (5, 15, 30, 60, 90, 120, 180, 240min), filtered through a 0.22 μm pinhole filter in a 10mL centrifuge tube, and the concentration of Sb (III) in the solution was determined in triplicate for all experimental samples and averaged.
As can be seen from FIG. 3, the removal of Sb (III) by A-nZVI is more rapid, the removal rate of Sb (III) reaches more than 95% 10min before the reaction, while nZVI is about 35%, and nZVI is unstable to Sb (III) removal during the reaction, and the removal rate is about 40% after 4h of reaction. The removal rate of Sb (III) by A-nZVI is far higher than that of nZVI and approaches to 100 percent.
Example 3
A150-ml glass bottle with a polyethylene screw cap was used as a reactor, and an aqueous Sb (III) solution (initial pH 4.8-5.0) was treated at a concentration of 50 mg/L. Measuring 100mL wastewater containing Sb (III) without adjusting the pH value of a water body; introducing 8min N2Removing dissolved oxygen, adding 0.02g A-nZVI particles, andthe reactor was placed on a constant temperature shaker at 25 + -0.2 deg.C, at a speed of 200r/min, for a period of 4 h. The solution was filtered and the concentration of Sb (III) in the solution was measured by ICP-OES.
Example 4
A150-ml glass bottle with a polyethylene screw cap was used as a reactor, and the treatment object was an aqueous Sb (III) solution (initial pH 4.8-5.0) at a concentration of 100 mg/L. Measuring 100mL wastewater containing Sb (III) without adjusting the pH value of a water body; introducing 8min N2Removing dissolved oxygen, adding 0.02g A-nZVI particles, and placing the reactor on a constant temperature shaking table, wherein the temperature is 25 +/-0.2 ℃, the rotating speed is 200r/min, and the reaction time is 4 h. The solution was filtered and the concentration of Sb (III) in the solution was measured by ICP-OES.
Example 5
A150-ml glass bottle with a polyethylene cap was used as a reactor, and the treatment object was an aqueous Sb (III) solution (initial pH 4.8-5.0) having a concentration of 150 mg/L. Measuring 100mL wastewater containing Sb (III) without adjusting the pH value of the water body; introducing 8min N2Removing dissolved oxygen, adding 0.02g A-nZVI particles, and placing the reactor on a constant temperature shaking table, wherein the temperature is 25 +/-0.2 ℃, the rotating speed is 200r/min, and the reaction time is 4 h. The solution was filtered and the concentration of Sb (III) in the solution was measured by ICP-OES.
Example 6
A150-ml glass bottle with a polyethylene screw cap was used as a reactor, and an aqueous Sb (III) solution having a concentration of 200mg/L (initial pH of 4.8 to 5.0) was treated. Measuring 100mL wastewater containing Sb (III) without adjusting the pH value of a water body; introducing 8min N2Removing dissolved oxygen, adding 0.02g A-nZVI particles, and placing the reactor on a constant temperature shaking table, wherein the temperature is 25 +/-0.2 ℃, the rotating speed is 200r/min, and the reaction time is 4 h. The solution was filtered and the concentration of Sb (III) in the solution was measured by ICP-OES.
Example 7
A150-ml glass bottle with a polyethylene screw cap was used as a reactor, and the treatment object was an aqueous Sb (III) solution (initial pH 4.8-5.0) having a concentration of 250 mg/L. Measuring 100mL wastewater containing Sb (III) without adjusting the pH value of a water body; introducing 8min N 2Removing dissolved oxygen, adding 0.02g A-nZVI particles, andthe reactor was placed on a constant temperature shaker at 25 + -0.2 deg.C, at a speed of 200r/min, for a period of 4 h. The solution was filtered and the concentration of Sb (III) in the solution was measured by ICP-OES.
Specific results are shown in table 1 and fig. 4.
TABLE 1 removal rates of five initial concentrations Sb (III)
As can be seen from table 1 and fig. 4, the lower the initial sb (iii) concentration is, the higher the sb (iii) removal rate is.
Example 8
A150-ml glass bottle with a polyethylene screw cap was used as a reactor, and the treatment object was an aqueous Sb (III) solution (initial pH 4.8-5.0) at a concentration of 100 mg/L. Measuring 100mL of wastewater containing Sb (III), and adjusting the pH value of a water body to 3.0 by using 0.1mol/L hydrochloric acid and 0.1mol/L sodium hydroxide; introducing 8min N2Removing dissolved oxygen, adding 0.02g A-nZVI, covering and sealing, and placing the reactor on a constant temperature shaking table, wherein the temperature is 25 +/-0.2 ℃, the rotating speed is 200r/min, and the reaction time is 4 h. The solution was filtered and the concentration of Sb (III) in the solution was measured by ICP-OES.
Example 9
A150-ml glass bottle with a polyethylene screw cap was used as a reactor, and the treatment object was an aqueous Sb (III) solution (initial pH 4.8-5.0) at a concentration of 100 mg/L. Measuring 100mL of wastewater containing Sb (III), and adjusting the pH value of a water body to 5.0 by using 0.1mol/L hydrochloric acid and 0.1mol/L sodium hydroxide; introducing 8min N 2Removing dissolved oxygen, adding 0.02g A-nZVI, sealing, and placing the reactor on a constant temperature shaking table at 25 + -0.2 deg.C and 200r/min for 4 h. The solution was filtered and the concentration of Sb (III) in the solution was measured by ICP-OES.
Example 10
Using bodies with polyethylene nutsA150 ml glass bottle was used as a reactor, and the object to be treated was an aqueous Sb (III) solution (initial pH 4.8-5.0) having a concentration of 100 mg/L. Measuring 100mL of wastewater containing Sb (III), and adjusting the pH value of a water body to 7.0 by using 0.1mol/L hydrochloric acid and 0.1mol/L sodium hydroxide; introducing 8min N2Removing dissolved oxygen, adding 0.02g A-nZVI, covering and sealing, and placing the reactor on a constant temperature shaking table, wherein the temperature is 25 +/-0.2 ℃, the rotating speed is 200r/min, and the reaction time is 4 h. The solution was filtered and the concentration of Sb (III) in the solution was measured by ICP-OES.
Example 11
A150-ml glass bottle with a polyethylene screw cap was used as a reactor, and the treatment object was an aqueous Sb (III) solution (initial pH 4.8-5.0) at a concentration of 100 mg/L. Measuring 100mL of wastewater containing Sb (III), and adjusting the pH value of a water body to 9.0 by using 0.1mol/L hydrochloric acid and 0.1mol/L sodium hydroxide; introducing 8min N2Removing dissolved oxygen, adding 0.02g A-nZVI, covering and sealing, and placing the reactor on a constant temperature shaking table, wherein the temperature is 25 +/-0.2 ℃, the rotating speed is 200r/min, and the reaction time is 4 h. The solution was filtered and the concentration of Sb (III) in the solution was measured by ICP-OES.
Example 12
A150-ml glass bottle with a polyethylene screw cap was used as a reactor, and the treatment object was an aqueous Sb (III) solution (initial pH 4.8-5.0) at a concentration of 100 mg/L. Measuring 100mL of wastewater containing Sb (III), and adjusting the pH value of a water body to 11.0 by using 0.1mol/L hydrochloric acid and 0.1mol/L sodium hydroxide; introducing 8min N2Removing dissolved oxygen, adding 0.02g A-nZVI, covering and sealing, and placing the reactor on a constant temperature shaking table, wherein the temperature is 25 +/-0.2 ℃, the rotating speed is 200r/min, and the reaction time is 4 h. The solution was filtered and the concentration of Sb (III) in the solution was measured by ICP-OES.
Specific results are shown in table 2 and fig. 5.
TABLE 2 removal rates of five pH values Sb (III)
As is clear from Table 2 and FIG. 5, the removal rate of Sb (III) hardly changed when the pH was 5 or more.
Example 13
A150-ml glass bottle with a polyethylene screw cap was used as a reactor, 100ml of 100mg/L aqueous Sb (III) solution (initial pH 4.8-5.0) was introduced thereinto, and 8min of N was passed therethrough2Removing dissolved oxygen, adding 0.05g A-nZVI, sealing, and performing adsorption reaction at normal temperature (25 + -0.2 deg.C) in a shaker at 200r/min for 4 hr. After the reaction is finished, the A-nZVI particles adsorbing Sb (III) are collected, soaked in 0.1mol/L NaOH solution (100mL) for 4 hours at 200rpm to desorb the Sb (III), then centrifuged, washed by deionized water, and the process is repeated three times. And finally, evaluating the recovery performance of the recovered particles, wherein the cycle number is 5, and the specific operation is as follows:
A150-ml glass bottle with a polyethylene screw cap was used as a reactor, and the treatment object was an aqueous Sb (III) solution (initial pH 4.8-5.0) at a concentration of 100 mg/L. Measuring 100mL wastewater containing Sb (III) without adjusting the pH value of a water body; introducing 8min N2Removing dissolved oxygen, adding the collected A-nZVI particles (the particles recovered above), and placing the reactor on a constant temperature shaking table, wherein the temperature is 25 +/-0.2 ℃, the rotating speed is 200r/min, and the reaction time is 4 h. The solution was filtered and the concentration of Sb (III) in the solution was measured by ICP-OES.
The results are shown in Table 3 and FIG. 6.
TABLE 3 cycling stability
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The preparation method of the amorphous nano zero-valent iron is characterized by comprising the following steps of:
under the protection of nitrogen or inert gas, adding ethylenediamine into the ferric salt solution, uniformly mixing, adding a reducing agent, and stirring for reaction to obtain the amorphous nano zero-valent iron.
2. The method for preparing the amorphous nanoscale zero-valent iron according to claim 1, wherein the molar ratio of iron in the ethylenediamine and the iron salt is 2.5: 1-3.5: 1; the molar ratio of the reducing agent to iron in the iron salt is 25: 9-50: 9.
3. the method for preparing the amorphous nano zero-valent iron according to claim 1, wherein the iron salt in the iron salt solution is ferric chloride; the reducing agent is NaBH4。
4. The method for preparing the amorphous nanoscale zero-valent iron according to claim 1, wherein the reducing agent is added dropwise at a rate of 40-50 mL/min; and after the addition of the reducing agent is finished, continuously stirring for reaction for 10-20 minutes.
5. The method for preparing the amorphous nano zero-valent iron according to claim 1, wherein the concentration of the iron salt solution is 0.045-0.055 mol/L, and the solvent is water;
the reducing agent is added in the form of reducing agent solution with the concentration of 0.2-0.3 mol/L, and the solvent is water.
6. An amorphous nano zero-valent iron prepared by the method of any one of claims 1 to 5.
7. The use of the amorphous nano zero-valent iron of claim 6 for removing trivalent antimony from a body of water.
8. The application of the amorphous nano zero-valent iron in removing trivalent antimony in a water body according to claim 7, is characterized in that the amorphous nano zero-valent iron is added into a trivalent antimony-containing water body with the pH value of 3-11 and removed by oscillation.
9. The application of the amorphous nanoscale zero-valent iron in removing trivalent antimony in a water body according to claim 8, wherein the pH is 5-11; the concentration of the trivalent antimony in the water body is 50-250 mg/L; the mass volume ratio of the amorphous nano zero-valent iron to the water body is 0.02-0.05 g: 100-500 mL.
10. The application of the amorphous nanoscale zero-valent iron in removing trivalent antimony in a water body according to claim 8, wherein the oscillation is constant-temperature oscillation; the temperature is 25 +/-0.2 ℃; the oscillation reaction time is not less than 4 h; the oscillation speed is 200 r/min;
the vibration removal is carried out under a closed condition, and the oxygen removal treatment is carried out by introducing nitrogen or inert gas before the amorphous nano zero-valent iron is added.
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