CN115739034A - Chitin microsphere loaded nano zero-valent iron material and preparation method and application thereof - Google Patents
Chitin microsphere loaded nano zero-valent iron material and preparation method and application thereof Download PDFInfo
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- CN115739034A CN115739034A CN202211362258.7A CN202211362258A CN115739034A CN 115739034 A CN115739034 A CN 115739034A CN 202211362258 A CN202211362258 A CN 202211362258A CN 115739034 A CN115739034 A CN 115739034A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 168
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- 239000004005 microsphere Substances 0.000 title claims abstract description 132
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- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 claims description 7
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- 229910052742 iron Inorganic materials 0.000 abstract description 31
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- WOSISLOTWLGNKT-UHFFFAOYSA-L iron(2+);dichloride;hexahydrate Chemical compound O.O.O.O.O.O.Cl[Fe]Cl WOSISLOTWLGNKT-UHFFFAOYSA-L 0.000 abstract 1
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
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Abstract
The invention provides a chitin microsphere loaded nano zero-valent iron material and a preparation method and application thereof. The preparation method comprises dispersing chitin powder in sodium hydroxide/urea water mixed system, dissolving by freezing-thawing cycle to obtain chitin solution, emulsifying-heating to obtain emulsion, and washing with deionized water and ethanol to obtain chitin microspheres; adding into ethanol aqueous solution of iron chloride hexahydrate, and introducing nitrogenAdding KBH 4 The solution containing Na 2 S 2 O 4 KBH of 4 And carrying out liquid phase reduction on the solution to obtain the chitin microsphere loaded nano zero-valent iron. The chitin microspheres prepared by dissolving the alkali/urea low-temperature solvent system have unique nano fibers and porous structures, and rich hydroxyl groups and acetamido groups in molecular chains can effectively fix metallic iron, so that the defect that nano zero-valent iron is easy to oxidize and agglomerate is overcome, and the activity and the capability of recycling the nano zero-valent iron are improved.
Description
Technical Field
The invention belongs to the technical field of environmental pollution remediation, and particularly relates to a chitin microsphere loaded nano zero-valent iron material as well as a preparation method and application thereof.
Background
The increasing industrialization and urbanization cause more and more wastewater containing heavy metals and organic pollutants to be directly discharged into water environment, thus causing water pollution. Water pollution not only harms the ecological environment, but also causes hidden dangers to human health, and among numerous heavy metal pollutants, hexavalent chromium (Cr (VI)) becomes a representative pollution element. Chromium is usually present in the environment as Cr (III) and Cr (VI), which have strong toxicity and pose serious hazards to human health and ecological environment. Nitrobenzene (NB) is widely used as an organic compound in various industrial fields such as explosives, pesticides, and organic synthetic intermediates. Due to their high toxicity, carcinogenicity, teratogenicity and resistance to biodegradation, nitrobenzene has become one of the major organic pollutants in environmental waters. Therefore, the development of technologies and materials for efficiently removing heavy metals and organic pollutants in water bodies becomes an urgent problem to be solved.
Compared with the common wastewater treatment methods (such as adsorption, membrane separation and ion exchange), the nano zero-valent iron is widely applied to removing pollutants in water due to the strong reducibility, no toxicity and harm to human bodies and environment, safety and stability and the like. However, due to the strong magnetic field force and the high surface energy, the nano zero-valent iron particles are seriously agglomerated, so that the reaction activity is remarkably reduced, and the application of the nano zero-valent iron particles is limited.
Disclosure of Invention
The invention aims to provide a chitin microsphere loaded nano zero-valent iron material, and a preparation method and application thereof, aiming at the defects in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
the first purpose of the invention is to provide a preparation method of a chitin microsphere loaded nano zero-valent iron material, which comprises the following steps:
step S1, dispersing chitin powder in a sodium hydroxide/urea water mixed system, dissolving through freezing-unfreezing circulation to obtain a chitin solution, emulsifying and heating the chitin solution to obtain an emulsion, and washing the emulsion with deionized water and ethanol to obtain chitin microspheres;
step S2, in the pre-configured FeCl 3 ·6H 2 Adding the chitin microspheres obtained in the step S1 into an O ethanol aqueous solution, and adding Na containing 0-2.5 mmol under the condition of introducing nitrogen 2 S 2 O 4 KBH of 4 And obtaining the chitin microsphere loaded nano zero-valent iron material by a liquid phase reduction principle.
Furthermore, the size of the chitin microspheres is 5-50 mu m.
Further, in step S2, the FeCl is 3 ·6H 2 The concentration of the O ethanol water solution is 0.009 mol/L-0.45 mol/L; the KBH 4 The solution concentration is 0.045 mol/L-2.25 mol/L, and the chitin microspheres and the FeCl 3 ·6H 2 The mass molar ratio of O is 1g: (0.0018-0.09) mol.
Further, the KBH 4 The solution contains Na 2 S 2 O 4 The molar weight of (b) is 0.5-2.5 mmol.
Further, in step S1, in the sodium hydroxide/urea-water mixed system, the mass fractions of sodium hydroxide, urea and water are 7 to 12%,3 to 6% and 82 to 90%; the mass of the chitin powder is 4-7% of the mass of the mixed system, the freezing temperature is-40-25 ℃, the freezing time is 3-8 hours, the thawing temperature is 15-35 ℃, and the cycle time is 1-4 times.
Further, in step S1, the process of emulsifying and heating the chitin solution is as follows: adding the chitin solution into isooctane containing span 85, stirring for 0.5-2 h, adding tween 85, continuously stirring for 0.5-2 h, heating to 80-100 ℃ after stirring, and adjusting the pH of the solution to be 7 +/-0.5.
Further, the mass fraction of the span 85 in the isooctane is 0.5-5 parts, the mass fraction of the tween 85 in the isooctane is 0.3-3 parts, and the mass fraction of the chitin solution in the isooctane is 5-20 parts.
The second purpose of the invention is to provide the chitin microsphere loaded nano zero-valent iron material prepared by the preparation method.
The third purpose of the invention is to provide the chitin microsphere loaded nano zero-valent iron material applied to the degradation and removal of hexavalent chromium in water.
The fourth purpose of the invention is to provide the chitin microsphere loaded nano zero-valent iron material applied to the degradation and removal of hexavalent chromium and nitrobenzene composite pollutants in water.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
(1) According to the chitin microsphere loaded nano zero-valent iron material provided by the invention, chitin has excellent thermal/chemical stability and can resist dilute acid, alkali and various organic solvents, the chitin microsphere prepared by dissolving an alkali/urea low-temperature solvent system has unique nanofiber and porous structure, and abundant hydroxyl and acetamido groups in a molecular chain of the chitin microsphere can effectively rivet metal iron, so that the defect that nano zero-valent iron is easy to oxidize and agglomerate is improved, and the activity and the capability of recycling the nano zero-valent iron are improved;
(2) The preparation method of the invention utilizes the chitin microspheres as a carrier and the nano zero-valent iron as a catalyst to synthesize the chitin microsphere loaded nano zero-valent iron and the chitin microsphere loaded vulcanized nano zero-valent iron composite material, has the advantages of strong reaction activity, high catalytic efficiency and recyclability, can efficiently remove heavy metals and organic pollutants in water, can be biodegraded, and cannot cause secondary pollution;
(3) The chitin microsphere loaded with the nano zero-valent iron material can be used for adsorbing and removing heavy metal ions, and can be used as a supporting material to effectively disperse and fix nano zero-valent iron and modified particles thereof and inhibit aggregation and passivation of the nano zero-valent iron and the modified particles thereof, so that the reductive reaction activity of the nano zero-valent iron material is improved, and the efficiency of the zero-valent iron material in removing complex pollutants is further improved.
Drawings
FIG. 1a is a scanning electron micrograph of chitin microspheres;
FIG. 1b is a scanning electron microscope image of chitin microsphere-loaded sulfurized nano zero-valent iron;
FIG. 1c is an EDS diagram of chitin microsphere-supported sulfurized nano zero-valent iron;
FIG. 1d is a BET plot of chitin powder;
FIG. 1e is a BET diagram of chitin microspheres;
FIG. 2 is a diagram showing the effect of removing mixed pollution of hexavalent chromium and nitrobenzene by using chitin microspheres loaded with nanoscale zero-valent iron, chitin microspheres and different iron microsphere mass ratios;
FIG. 3 is a diagram showing the effect of removing hexavalent chromium by using nano zero-valent iron, chitin microspheres, chitin microsphere-loaded nano zero-valent iron and chitin microsphere-loaded vulcanized nano zero-valent iron with different ratios of sulfur to iron.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following detailed description of the embodiments of the present invention is provided in conjunction with the accompanying drawings. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The solution used in the present invention can be prepared in various ways, such as the following ways:
11% sodium hydroxide/4% urea/85% water mixed system: for example, a mixed solution may be prepared by weighing 11g of NaOH,4g of urea and 85g of water.
FeCl 3 ·6H 2 O ethanol aqueous solution: for example, a certain mass of FeCl can be weighed 3 ·6H 2 Dissolving O in 100ml of 30% (v/v) ethanol water solution;
KBH 4 solution: for example, a certain mass of KBH may be weighed 4 Dissolved in 100ml of ice water (adjusted to pH 10-11 with 5wt% aqueous NaOH);
containing Na 2 S 2 O 4 KBH of 4 Solution: for example, a certain mass of KBH may be weighed 4 And Na 2 S 2 O 4 Dissolved in 100ml of ice water (adjusted to pH 10-11 with 5wt% aqueous NaOH);
the chitin powder used in the invention is a commercial product, and the quality standard of the chitin powder is not lower than that of food grade.
In some embodiments, the chitin powder can be further purified to achieve food grade, and the purification process is as follows: stirring a certain amount of chitin powder in NaOH aqueous solution with a certain mass concentration at room temperature for not less than 12h to remove residual protein, and rinsing with distilled water to neutrality. Stirring the filtered chitin powder in a commercial hydrochloric acid solution with volume concentration at room temperature for not less than 24h to remove residual minerals. Rinsing with distilled water to neutrality. And the solid obtained by filtering is stirred in NaOH aqueous solution with certain mass concentration for no less than 24 hours at room temperature. Rinsing with distilled water to neutrality. Then H at a certain mass concentration 2 O 2 Stirring the solution (adding NaOH to adjust pH to 8-9) at 80 deg.C for no less than 6 hr to remove pigment, rinsing for multiple times, and vacuum drying to obtain purified chitin powder.
Example 1
Preparing a chitin microsphere loaded nano zero-valent iron material with an iron/microsphere mass ratio = 0.1:
step S1, preparation of chitin microspheres
Dispersing 6g chitin powder in a mixed system of 11% sodium hydroxide, 4% urea and 85% water, thawing in a cold trap at-40 deg.C for 8h at room temperature of 15 deg.C, and repeating the freezing-thawing process for 2 times to obtain clear and transparent chitin solution. Adding 20g of chitin solution into 100g of isooctane containing 2.2g of span 85, stirring for 1h, then adding 1.2g of Tween 85, and continuing stirring for 1h. After completion of the stirring, heating to 85 ℃ and adjusting the solution to pH =7 with 5wt% aqueous HCl solution to obtain chitin microspheres, washing with deionized water and ethanol, observing the microsphere shape size by an optical microscope and counting the particle size distribution to obtain chitin microspheres having a size distribution of 10-30 μm.
Step S2, preparation of chitin microsphere loaded nano zero-valent iron material
Weighing 0.5g of chitin microspheres prepared in the step S1, and adding 100mL of 0.009mol/L FeCl 3 ·6H 2 Placing the O ethanol water solution in a constant temperature oscillator for 12h at room temperature to fully adsorb; then transferred to a nitrogen-filled three-neck flask, and 100mL of 0.045mol/L KBH was added 4 Stirring the solution for 120min to allow the solution to react fully until bubbles are stopped generating in the reaction vessel; and pouring out the upper layer solution, and alternately washing the upper layer solution with deoxidized deionized water and deoxidized absolute ethyl alcohol for three times to obtain the chitin microsphere loaded nano zero-valent iron material with the iron/microsphere mass ratio = 0.1.
As shown in fig. 1a, the chitin microspheres are round microspheres, and the surfaces of the microspheres have nanofiber structures. The nanofiber structure is caused by heat-induced self-assembly of chitin molecules in the regeneration process from a NaOH/urea solvent, so that the chitin microspheres have higher surface area and are easier to obtain chelating sites for metal ions.
As shown in FIG. 1d and FIG. 1e, the BET nitrogen adsorption method was used to analyze the specific surface areas of the chitin powder and the chitin microspheres, and the results showed that the BET specific surface area of the chitin microspheres was 123m 2 The volume/g is in accordance with the adsorption-desorption isotherm of the microporous/mesoporous material, and a hysteresis loop exists; the BET specific surface area of the chitin powder is only 6.16m 2 The chitosan microsphere obtained by dissolving has finer surface texture and higher specific surface area than pure chitin powder.
Example 2
Preparation of chitin microsphere-loaded nano zero-valent iron material with iron/microsphere mass ratio =0.5
0.5g of chitin microspheres prepared in step S1 of example 1 was weighed, and 100mL of 0.045mol/L FeCl was added 3 ·6H 2 Placing the O ethanol water solution in a constant temperature oscillator for 12h at room temperature to fully adsorb; then transferred to a nitrogen-filled three-neck flask, and 100mL of 0.225mol/L KBH was added 4 Stirring the solution at 600rpm for 120min to react fully until the reaction volume is reachedStopping generating bubbles in the device; and pouring out the upper layer solution, and alternately washing the upper layer solution with deoxidized deionized water and deoxidized absolute ethyl alcohol for three times to obtain the chitin microsphere loaded nano zero-valent iron material with the iron/microsphere mass ratio = 0.5.
Example 3
Preparation of chitin microsphere loaded nano zero-valent iron material with iron/microsphere mass ratio =1
0.5g of chitin microspheres prepared in step S1 of example 1 is weighed, and 100mL of 0.09mol/L FeCl is added 3 ·6H 2 Placing the O ethanol water solution in a constant temperature oscillator for 12 hours at room temperature to fully adsorb; then transferred to a nitrogen-filled three-neck flask, and 100mL of 0.45mol/L KBH was added 4 Stirring the solution at the speed of 600rpm for 120min to react fully until bubbles are stopped generating in the reaction vessel; and pouring out the upper layer solution, and alternately washing the upper layer solution with deoxidized deionized water and deoxidized absolute ethyl alcohol for three times to obtain the chitin microsphere loaded nano zero-valent iron material with the iron/microsphere mass ratio = 1.
Example 4
Preparation of chitin microsphere loaded nano zero-valent iron material with iron/microsphere mass ratio =5
0.5g of chitin microspheres prepared in step S1 of example 1 is weighed, and 100mL of 0.45mol/L FeCl is added 3 ·6H 2 Placing the O ethanol water solution in a constant temperature oscillator for 12 hours at room temperature to fully adsorb; then transferred to a nitrogen-filled three-neck flask, and 100mL of 2.25mol/L KBH was added 4 Stirring the solution at the speed of 600rpm for 120min to fully react until bubbles are not generated in the reaction vessel; and pouring out the upper layer solution, and alternately washing the upper layer solution with deoxidized deionized water and deoxidized absolute ethyl alcohol for three times to obtain the chitin microsphere loaded nano zero-valent iron material with the iron/microsphere mass ratio = 5.
Example 5
Preparing a chitin microsphere loaded vulcanized nano zero-valent iron material with a sulfur/iron molar ratio = 0:
0.5g of chitin microspheres prepared in step S1 of example 1 was weighed, and 100ml of 0.1mol/L FeCl was added 3 ·6H 2 O ethanol in water in the presence ofPlacing the mixture in a constant temperature oscillator for 12 hours at room temperature to fully adsorb the mixture; centrifuging for many times to separate out redundant Fe 3+ A solution; then transferred to a nitrogen-filled three-neck flask, and 100mL of 0.5mol/L KBH is added 4 Solution (containing 0mmol of Na) 2 S 2 O 4 ) Stirring at 300rpm for 120min to react completely until no bubble is generated in the reaction container; and pouring out the upper layer solution, and alternately washing the upper layer solution with deoxidized deionized water and deoxidized absolute ethyl alcohol for three times to obtain the chitin microsphere loaded nano zero-valent iron material with the sulfur/iron molar ratio =0.
Example 6
Preparation of chitin microsphere supported sulfurized nano zero-valent iron material with sulfur/iron molar ratio = 0.25:
0.5g of chitin microspheres prepared in step S1 of example 1 was weighed, and 100ml of 0.1mol/L FeCl was added 3 ·6H 2 Placing the O ethanol water solution in a constant temperature oscillator for 12h at room temperature to fully adsorb; centrifuging for many times to separate out redundant Fe 3+ A solution; then transferred to a nitrogen-filled three-neck flask, and 100mL of 0.5mol/L KBH is added 4 Solution (containing 2.5mmol of Na) 2 S 2 O 4 ) Stirring at 300rpm for 120min to react completely until bubbles are generated in the reaction container; and pouring out the upper solution, and alternately washing the solution with the deoxidized deionized water and the deoxidized absolute ethyl alcohol for three times to obtain the chitin microsphere loaded vulcanized nano zero-valent iron material with the sulfur/iron molar ratio = 0.25.
Example 7
Preparing a chitin microsphere loaded vulcanized nano zero-valent iron material with the sulfur/iron molar ratio = 0.05:
0.5g of chitin microspheres (10-30 μm) prepared in step S1 of example 1 was weighed, and 100ml of 0.1mol/L FeCl was added 3 ·6H 2 Placing the O ethanol water solution in a constant temperature oscillator for 12h at room temperature to fully adsorb; centrifuging for many times to separate out redundant Fe 3+ A solution; then transferred to a nitrogen-filled three-neck flask, and 100mL of 0.5mol/L KBH is added 4 Solution (containing 0.5mmol of Na) 2 S 2 O 4 ) Speed of stirringAt 300rpm, stirring for 120min to allow the mixture to fully react until bubbles stop generating in the reaction vessel; and pouring out the upper layer solution, and alternately washing the upper layer solution with deoxidized deionized water and deoxidized absolute ethyl alcohol for three times to obtain the chitin microsphere loaded vulcanized nano zero-valent iron material with the sulfur/iron molar ratio = 0.05.
FIG. 1b shows an SEM image of chitin microsphere-supported sulfurized nano zero-valent iron. The microspherical shape of the chitin microsphere loaded vulcanized nano zero-valent iron with a nano fiber structure is kept unchanged. Meanwhile, no large amount of naked S-nZVI is gathered around the microsphere from the aspects of a scanning electron microscope and an optical image, which indicates that most S-nZVI particles are fixed on the Chi-M surface. Due to the small volume of S-nZVI, the distribution of S-nZVI on chitin microspheres was further studied by SEM-EDS.
And fig. 1c shows the regional EDS spectrum of the chitin microsphere loaded with the sulfurized nano zero-valent iron. In the EDS spectrogram, signals of C, N and O in chitin and signals of S and Fe in S-nZVI appear, which indicates that the chitin, the N and the O coexist on the surface of the microsphere.
Example 8
Preparing a chitin microsphere loaded vulcanized nano zero-valent iron material with a sulfur/iron molar ratio =0.05 by using 5-10 mu m chitin microspheres:
step S1, preparation of chitin microspheres
Dispersing 4g of chitin powder in a mixed system of 7% sodium hydroxide, 6% urea and 87% water, thawing the mixture in a cold trap at the temperature of 25 ℃ below zero for 4 hours at the temperature of 35 ℃ below zero, and repeating the freezing-thawing process for 4 times to obtain a clear and transparent chitin solution. Adding 5g of chitin solution into 50g of isooctane containing 5g of span 85, stirring for 1h, then adding 3g of Tween 85, and continuing stirring for 1h. After stirring, heating to 85 ℃, adjusting the solution to pH =7 by using 5wt% aqueous HCl solution to obtain emulsion, washing with deionized water and ethanol, observing the microspherical size through an optical microscope and counting the particle size distribution to obtain chitin microspheres with the size distribution of 5-10 μm.
Step S2, weighing 0.5g of chitin microspheres prepared in the step S1, and adding 100ml of 0.1mol/L FeCl 3 ·6H 2 O ethanol water solution, under the condition of room temperature,placing in a constant temperature oscillator for 12h to make it sufficiently adsorb; centrifuging for many times to separate out redundant Fe 3+ A solution; then transferred into a three-neck flask filled with nitrogen, and added with 100mL of 0.5mol/L KBH 4 Solution (containing 0.5mmol of Na) 2 S 2 O 4 ) Stirring at 300rpm for 120min to react completely until bubbles are generated in the reaction container; and pouring out the upper solution, and alternately washing the solution with the deoxidized deionized water and the deoxidized absolute ethyl alcohol for three times to obtain the chitin microsphere loaded vulcanized nano zero-valent iron material with the sulfur/iron molar ratio = 0.05.
Example 9
Adopting chitin microspheres with 30-50 mu m chitin micro-preparation sphere sulfur/iron molar ratio =0.05 to load a vulcanized nano zero-valent iron material:
step S1, preparation of chitin microspheres
Dispersing 7g of chitin powder in a mixed system of 12% sodium hydroxide, 3% urea and 85% water, thawing in a cold trap at the temperature of-40 ℃ for 8h at the temperature of 15 ℃ at room temperature, and repeating the freezing-thawing process for 1 time to obtain a clear and transparent chitin solution. 10g of chitin solution is added into 50g of isooctane containing 0.5g of span 85 and stirred for 1 hour, and then 0.3g of Tween 85 is added and the stirring is continued for 1 hour. After completion of the stirring, heating to 85 ℃ was carried out, adjusting the solution to pH =7 with 5wt% aqueous HCl solution to obtain an emulsion, washing with deionized water and ethanol, observing the microsphere-shaped size by an optical microscope and counting the particle size distribution to obtain chitin microspheres having a size distribution of 30 to 50 μm.
Step S2, weighing 0.5g of chitin microspheres prepared in the step S1, and adding 100ml of 0.1mol/L FeCl 3 ·6H 2 Placing the O ethanol water solution in a constant temperature oscillator for 12 hours at room temperature to fully adsorb; centrifuging for many times to separate out redundant Fe 3+ A solution; then transferred to a nitrogen-filled three-neck flask, and 100mL of 0.5mol/L KBH is added 4 Solution (containing 0.5mmol of Na) 2 S 2 O 4 ) Stirring at 300rpm for 120min to react completely until no bubble is generated in the reaction container; pouring out the upper solution, and alternately washing the upper solution with deoxidized deionized water and deoxidized absolute ethyl alcohol for three timesAnd obtaining the chitin microsphere loaded vulcanized nano zero-valent iron material with the sulfur/iron molar ratio = 0.05.
Comparative example 1
Preparing a nano zero-valent iron material:
as a comparative group, a nano zero-valent iron material not supported on the chitin microspheres was prepared: 100ml of 0.01mol/L FeCl 3 ·6H 2 Placing the O solution in a constant temperature oscillator to oscillate uniformly at room temperature; then transferred into a three-neck flask filled with nitrogen, and added with 0.05mol/L KBH with the same volume 4 Stirring the solution at the speed of 600rpm for 30min to react fully until bubbles are stopped generating in the reaction vessel; and pouring out the upper layer solution, and alternately washing the upper layer solution with the deoxidized deionized water and the deoxidized absolute ethyl alcohol for three times to obtain the nano zero-valent iron material.
Comparative example 2
Preparing a chitin microsphere material:
chitin microspheres prepared in step S1 of example 1 were used.
In order to better illustrate the effect of the chitin microsphere loaded with the nano zero-valent iron material in degrading heavy metals and organic pollutants, the applicant also carries out the following research:
1. research on removal rate of chitin microsphere loaded nano zero-valent iron material prepared by different iron/microsphere ratios to Cr (VI) and nitrobenzene simultaneously
0.1g of each of the chitin microspheres loaded with the nano zero-valent iron materials prepared in examples 1, 2, 3 and 4 was weighed, placed in 100ml of a mixed solution of 20mg/L Cr (VI) and nitrobenzene, and shaken in a shaking table at 150rpm and 25 ℃, the reaction time was 360min, after the reaction started, 2.5ml of samples were taken at 0min,5min,10min,15min,30min,60min,120min,180min and 360min, the samples were filtered through a 0.22 μ M filter membrane, and the concentration of Cr (VI) was measured by a microplate reader (Tecan M200 PRO, switzerland) ultraviolet-visible spectrophotometry, and nitrobenzene was measured by a liquid chromatograph.
As shown in fig. 2a and 2b, after 15min, the removal rates of the chitin microsphere-loaded nano zero-valent iron Cr (vi) with the iron/microsphere mass ratios =0.1, 0.5, 1, and 5 are 22.6%,78.03%,100%, and 58%, and the removal rates of nitrobenzene are 7.68%,52.39%,97.30%, and 42.65%, respectively.
2. Research on removal rate of chitin microspheres for Cr (VI) and nitrobenzene simultaneously
0.05g of the chitin microspheres prepared in example 1 was placed in 100ml of a mixed solution of 20mg/L of Cr (VI) and nitrobenzene, the mixed solution was shaken in a shaking table at 150rpm and 25 ℃ for 360min, the reaction was started at 0min,5min,10min,30min,60min,120min,180min, and 360min, 2.5ml of the sample was sampled, the sample was filtered through a 0.22 μ M filter membrane, and the concentration of Cr (VI) was measured by a microplate reader (Tecan M200 PRO, switzerland) ultraviolet-visible spectrophotometry, and nitrobenzene was measured by a liquid chromatograph.
As shown in fig. 2a and 2b, the chitin microspheres have little effect on removing mixed pollution of hexavalent chromium and nitrobenzene.
3. Research on removal rate of nano zero-valent iron on Cr (VI) and nitrobenzene simultaneously
0.05g of the nano zero-valent iron prepared in the comparative example 1 is placed in 100ml of a mixed solution of 20mg/L of Cr (VI) and nitrobenzene and is placed in a shaking table at 150rpm and 25 ℃ for oscillation, the reaction time is 360min, 2.5ml of samples are taken at 0min,5min,10min,15min,30min,60min,120min,180min and 360min after the reaction is started, the samples are filtered by a 0.22 mu M filter membrane, and the concentration of the Cr (VI) is measured by an enzyme-linked immunosorbent assay (Tecan M200 PRO, switzerland) ultraviolet-visible spectrophotometry, nitrobenzene and a liquid chromatograph.
As shown in FIGS. 2a and 2b, the Cr (VI) removal rate was 55.23% and the nitrobenzene removal rate was 43.9% after 15 min. Removing hexavalent chromium from the nano zero-valent iron, firstly, rapidly adsorbing the hexavalent chromium on the outer surface of the nano zero-valent iron, and obtaining electrons generated by the nano zero-valent iron from the adsorbed hexavalent chromium. In the process, along with the generation of a large amount of electrons on the surface of the nano zero-valent iron, the absorbed hexavalent chromium is reduced into trivalent chromium through hydrogenation. At the same time, a large amount of electrons and Fe 2+ Is released into solution. And Fe 2+ Electrons can be released. Reducing the hexavalent chromium in the solution into trivalent chromium, and complexing the trivalent chromium and the trivalent iron in the solution to form iron-chromium coprecipitation so as to remove the hexavalent chromium.
The nitrobenzene is removed by the nano zero-valent iron, and the nitrobenzene is quickly adsorbed on the outer surface of the nano zero-valent iron. And secondly, the adsorbed nitrobenzene obtains electrons generated by the nano zero-valent iron. In the process, a large number of electrons are generated on the surface of the nano zero-valent iron, and the adsorbed NO in the nitrobenzene is absorbed 2 Aniline is produced by hydrogenation. Third, a large number of electrons and Fe 2+ Is released into solution. And Fe 2+ Electrons can be released. Nitrobenzene in solution accepts electrons and is ultimately reduced to aniline.
4. Research on removal rate of chitin microsphere loaded vulcanized nano zero-valent iron material to Cr (VI) with different sulfur/iron molar ratios
0.1g of each of the sulfurized nanoscale zero-valent iron-supported chitin microspheres prepared in examples 5, 6 and 7 was weighed, placed in 50ml of a solution of 10mg/L Cr (VI), placed in a shaking table at 150rpm and 25 ℃ for oscillation, the reaction time was 180min, 1ml of the solution was sampled at 0min,15min,30min,60min,120min and 180min after the reaction started, the sample was filtered through a 0.45 μ M filter membrane, and the concentration of Cr (VI) was measured by UV-visible spectrophotometry using a microplate reader (Tecan M200 PRO, switzerland).
As shown in fig. 3, the removal rates of chitin microsphere-loaded sulfurized nano zero-valent iron Cr (vi) with sulfur/iron molar ratios =0, 0.05, and 0.25 after 120min were 21.5%, 94.5%, and 98.1%, respectively.
5. Research on removal rate of chitin microsphere loaded vulcanized nano zero-valent iron material with same sulfur/iron molar ratio prepared from chitin microspheres with different sizes on Cr (VI)
0.1g of each of the sulfurized nano zero-valent iron-loaded microspheres prepared in example 7, example 8 and example 9 was weighed, and placed in 50ml of a solution of 10mg/L of Cr (VI), and the solution was shaken at 150rpm and 25 ℃ in a shaking table, the reaction time was 180min, 1ml of the solution was sampled at 0min,15min,30min,60min,120min and 180min after the reaction started, the sample was filtered through a 0.45 μ M filter membrane, and the concentration of Cr (VI) was measured by UV-visible spectrophotometry using a microplate reader (Tecan M200 PRO, switzerland).
The results were: under the same conditions of sulfur/iron molar ratio = 0.05:
50mL of chitin microsphere loaded sulfurized nano zero-valent iron prepared by using chitin microspheres with the size distribution of 10-30 mu m is removed, and the 120min removal rate of 10mg/LCr (VI) is 94.5%;
50mL of chitin microsphere-loaded sulfurized nanoscale zero-valent iron prepared by using chitin microspheres with the size distribution of 5-10 mu m is removed, and the 120-min removal rate of 10mg/LCr (VI) is 92.5%;
50mL of chitin microsphere-loaded sulfurized nanoscale zero-valent iron prepared by using chitin microspheres with the size distribution of 30-50 μm is removed, and the 120-min removal rate of 10mg/LCr (VI) is 87.5%.
6. Research on removal rate of Cr (VI) by chitin microspheres
0.1g of chitin microspheres prepared in example 1 was placed in 50ml of 10mg/L Cr (VI) solution, shaken in a shaking table at 150rpm and 25 ℃ for 180min, 1ml of samples were taken at 0min,15min,30min,60min,120min and 180min after the start of the reaction, the samples were filtered through a 0.22 μ M filter, and the concentration of Cr (VI) was measured by UV-visible spectrophotometry using a microplate reader (Tecan M200 PRO, switzerland).
As shown in FIG. 2, the Cr (VI) removal rate after 120min was 41.83%.
7. Research on removal rate of nano zero-valent iron to Cr (VI)
0.005g of the nanoscale zero-valent iron prepared in comparative example 2 was placed in 50ml of a 10mg/L Cr (VI) solution, the solution was shaken in a 150rpm shaking table at 25 ℃ for 180min, 1ml of the solution was sampled at 0min,15min,30min,60min,120min,180min after the start of the reaction, the sample was filtered through a 0.22 μ M filter membrane, and the concentration of Cr (VI) was measured by UV-visible spectrophotometry using a microplate reader (Tecan M200 PRO, switzerland).
As shown in FIG. 2, the Cr (VI) removal rate after 120min was 47.8%.
8. Study on cyclic utilization of chitin microsphere loaded vulcanized nano zero-valent iron material
In example 6, 50ml and 10mg/LCr (VI) of chitin microsphere loaded sulfurized nano zero-valent iron with a sulfur/iron molar ratio =0.25 are removed for the first time, the removal rate is 99.9% after 180min, then the reacted solution is separated from the material in an anaerobic glove box, 50ml and 10mg/LCr (VI) which are freshly prepared are added, the removal rate is measured after 180min, the steps are repeated for three times, so that the efficiencies of repeatedly and circularly removing Cr (VI) from the chitin microsphere loaded sulfurized nano zero-valent iron are 99.8%,85.5% and 65.5% in sequence, the removal efficiency and the removal speed are reduced along with the increase of the cycle number, and the higher removal rate can be maintained, which indicates that the chitin microsphere loaded sulfurized nano zero-valent iron has the recycling value.
In summary, although the nano zero-valent iron particles are seriously agglomerated due to the stronger magnetic field force and the higher surface energy, the reaction activity is obviously reduced, the application is limited, and in order to overcome the agglomeration of the nano zero-valent iron, the chitin microspheres are introduced as the carrier. The chitin microspheres have large specific surface area, and rich hydroxyl and acetamido groups in molecular chains can effectively fix the nano zero-valent iron in a riveting mode, so that the defect that the nano zero-valent iron is easy to oxidize and agglomerate is overcome, the activity of the nano zero-valent iron is improved, and the removal efficiency of hexavalent chromium and nitrobenzene is greatly improved. And meanwhile, the nano zero-valent iron loaded on the surface of the chitin microspheres can be subjected to vulcanization modification, so that the activity and the electron transfer efficiency of the nano zero-valent iron are improved, and the removal efficiency of the nano zero-valent iron on hexavalent chromium is further enhanced.
The embodiments and features of the embodiments described herein above may be combined with each other without conflict.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a chitin microsphere loaded nano zero-valent iron material is characterized by comprising the following steps
The method comprises the following specific steps:
s1, dispersing chitin powder in a sodium hydroxide/urea water mixed system, and dissolving through freezing-unfreezing circulation to obtain a chitin solution, emulsifying and heating the chitin solution to obtain an emulsion, and washing the emulsion with deionized water and absolute ethyl alcohol to obtain chitin microspheres;
s2, in the pre-configured FeCl 3 ·6H 2 Adding the chitin microspheres obtained in the step S1 into an O ethanol aqueous solution, and adding Na containing 0-2.5 mmol of Na under the condition of introducing nitrogen 2 S 2 O 4 KBH of 4 And carrying out liquid phase reduction on the solution to obtain the chitin microsphere loaded nano zero-valent iron material.
2. The method of claim 1, wherein the size of the chitin microspheres is 5-50 μm.
3. The method of claim 1, wherein in step S2, the FeCl is 3 ·6H 2 The concentration of the O ethanol water solution is 0.009 mol/L-0.45 mol/L; the KBH 4 The solution concentration is 0.045 mol/L-2.25 mol/L, and the chitin microspheres and the FeCl 3 ·6H 2 The mass molar ratio of O is 1g: (0.0018-0.09) mol.
4. The method of claim 3, wherein the KBH is 4 The solution contains Na 2 S 2 O 4 The molar weight of (b) is 0.5-2.5 mmol.
5. The preparation method according to claim 1, wherein in step S1, the mass fractions of sodium hydroxide, urea and water in the sodium hydroxide/urea-water mixed system are 7 to 12%,3 to 6%, and 82 to 90%; the mass of the chitin powder is 4-7% of the mass of the mixed system, the freezing temperature is-40-25 ℃, the freezing time is 3-8 hours, the thawing temperature is 15-35 ℃, and the cycle time is 1-4 times.
6. The method of claim 1, wherein the step S1 comprises the steps of emulsifying and heating the chitin solution: adding the chitin solution into isooctane containing span 85, stirring for 0.5-2 h, then adding tween 85, continuously stirring for 0.5-2 h, heating to 80-100 ℃ after stirring, and adjusting the pH of the solution to be =7 +/-0.5.
7. The method according to claim 6, wherein the span 85 is 0.5 to 5 parts by mass of isooctane, the tween 85 is 0.3 to 3 parts by mass of isooctane, and the chitin solution is 5 to 20 parts by mass of isooctane.
8. The chitin microsphere loaded nano zero-valent iron material is characterized by being prepared by the preparation method of any one of claims 1 to 7.
9. The use of the chitin microsphere-loaded nanoscale zero-valent iron material of claim 8, wherein the use is for the degradation and removal of hexavalent chromium in water.
10. The application of the chitosan microsphere loaded nano zero-valent iron material of claim 8, which is applied to the degradation and removal of hexavalent chromium and nitrobenzene composite pollutants in a water body.
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