CN108014745B - Preparation method and application of nano magnetic iron-manganese oxide - Google Patents
Preparation method and application of nano magnetic iron-manganese oxide Download PDFInfo
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- CN108014745B CN108014745B CN201711411131.9A CN201711411131A CN108014745B CN 108014745 B CN108014745 B CN 108014745B CN 201711411131 A CN201711411131 A CN 201711411131A CN 108014745 B CN108014745 B CN 108014745B
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- 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
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a preparation method and application of a nano magnetic iron-manganese oxide, belonging to the field of material science and environmental engineering. By mixing FeCl2·4H2Dissolving O in a system of urea, ethanol and glycol, placing the system in a high-pressure reaction kettle, controlling the reaction temperature and time, and performing one-step synthesis to form magnetic Fe3O4Then mixing Fe3O4Soaking in potassium permanganate solution to obtain the magnetic Fe-based-Mn oxide nano material. The nano magnetic iron-based manganese oxide prepared by the method has good capacity of adsorbing heavy metal ions, and can remove Pb in lead-zinc tailings in a short time (1-5 min)2+And the sample has magnetism and is easy to separate; the iron and manganese source raw materials are rich and cheap, and are green and environment-friendly; provides a simple, convenient and efficient method for treating heavy metal ions, has good economic benefit and environmental benefit, and can be applied to large-scale production.
Description
Technical Field
The invention belongs to the field of material science and environmental engineering, and particularly relates to a preparation method and application of a nano magnetic iron-based manganese oxide.
Background
Lead is one of heavy metal elements with high toxicity in pollutants, has strong biological toxicity and biological enrichment effect, and can generate great toxic action on animals, plants and human beings. Lead has adverse effect on the form, production and photosynthesis of plants, reduces photosynthesis and respiration, reduces seed activity, inhibits growth and metabolism, and has strong inhibiting effect on soil urease and invertase. Lead is extremely harmful to the human body and is mainly neurotoxic. After entering the human body through the food chain, skin, respiratory tract system and digestive system, lead accumulates in the major organs of the human body such as liver, kidney, pancreas, artery and skeleton, causing irreversible damage to the nervous system, hematopoietic system, digestive system, cardiovascular system and immune system. After lead ions enter a human body, the lead ions enter tissues along with blood, and the brain capillaries and cerebral cortex are damaged, so that the symptoms of brain development retardation, insanity and the like are caused.
Lead used worldwide every year is about 4 x 106And only 1/4 is recycled, and most of the rest is discharged into the ecological environment in different forms, so that the environment is seriously polluted. Lead has the characteristics of concealment, long-term, accumulation, irreversible change and the like after entering the environment, and can be enriched through a food chain to seriously affect the health of human beings, so that the treatment of the lead in the wastewater is not slow.
Because the oxides of manganese have the characteristics of large specific surface area, good pore structure, high charge density and the like, and have strong adsorption effect on pollutants such as heavy metals, organic matters and the like in water, the oxides of manganese have more researches in treating heavy metal wastewater, and the oxides of manganese have the lead ion adsorption capacity which is more than 40 times that of the oxides of iron and have strong cation adsorption capacity specifically. The invention synthesizes Fe by one step3O4Then mixing Fe3O4Soaking in potassium permanganate solution to obtain the magnetic Fe-Mn oxide nanometer material with excellent capacity of adsorbing heavy metal lead ion.
Disclosure of Invention
The invention aims to provide a preparation method and application of a nano magnetic iron-based manganese oxide aiming at the defects of the existing preparation method of an adsorbing material. The nano magnetic iron-based manganese oxide prepared by the method can effectively remove heavy metal ions, has high removal rate, easy separation, environmental protection, good economic benefit and environmental benefit, low cost and simple operation.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation of the nano magnetic iron-manganese oxide comprises the following raw materials: urea, ferrous chloride tetrahydrate, hydrochloric acid, ethanol, ethylene glycol and potassium permanganate.
Specifically, the preparation method of the nano magnetic iron-manganese oxide comprises the following steps:
(1) dissolving urea in a mixed solution of absolute ethyl alcohol and hydrochloric acid (the volume ratio of the absolute ethyl alcohol to the hydrochloric acid is 12: 1), and stirring at room temperature until the urea is completely dissolved;
(2) adding ferrous chloride tetrahydrate (FeCl) into the solution obtained in the step (1)2·4H2O), continuously stirring;
(3) adding ethylene glycol into the solution obtained in the step (2), and continuing stirring;
(4) pouring the solution obtained in the step (3) into a high-pressure reaction kettle, and reacting for 2-6 h at a constant temperature of 160-180 ℃;
(5) cooling the solution reacted in the step (4) along with a furnace, and performing centrifugal separation, washing and drying (at 70-90 ℃) until the moisture is completely volatilized to obtain Fe3O4；
(6) Drying the Fe obtained in the step (5)3O4And (3) soaking in a potassium permanganate solution for 0.5h, performing centrifugal separation, washing, and vacuum drying (at 60-80 ℃) until the moisture is completely volatilized to obtain the magnetic iron-based-manganese oxide nano material.
The above FeCl2·4H2The concentration of O is 0.1-1.0 mol/L; the concentration of the potassium permanganate solution is 0.005-0.4 mol/L.
The magnetic iron-based-manganese oxide nano material prepared according to the technical scheme is applied to treatment of heavy metal ions, and shows a good removal effect.
The concrete application is as follows: taking a certain amount of wastewater containing heavy metal ions to be treated, putting the nano magnetic iron-manganese oxide into the wastewater, stirring, sampling at different times, centrifuging, and measuring the concentration of the heavy metal ions in clear liquid by using an atomic absorption spectrometer, wherein the total time is controlled within 10 min.
The invention is prepared by a simple redox impregnation method for the first time, and forms a core-shell structure with the inside being a magnetic iron-based compound and the outside being a manganese oxide nano thin shell, thereby endowing the original asexual Fe3O4Has good capability of adsorbing heavy metal ions, and can remove Pb in the lead-zinc tailings in a short time (1-5 min)2+And the sample has magnetism and is easy to separate; the iron and manganese source raw materials are rich and cheap, and are green and environment-friendly; provides a simple, convenient and efficient method for treating heavy metal ions, has good economic benefit and environmental benefit, and can be applied to large-scale production.
The invention has the following remarkable advantages:
(1) the preparation method is simple: firstly adopting a solvothermal method to synthesize Fe by one step3O4Then using KMnO4Solution soaking of Fe3O4Obtaining the magnetic iron-based-manganese oxide nano material; the process is simple to operate and low in cost;
(2) the sample is magnetic and easy to separate;
(3) green and environment-friendly: iron and manganese are used as environment-friendly elements, are low in price compared with other noble metal elements, and are wide in source, and the prepared magnetic iron-based manganese oxide nano material is heavy metal ion Pb2+The treatment of (2) showed a remarkable effect.
Drawings
FIG. 1 is an XRD pattern of the nano-materials of comparative example and examples 1-3 of the present invention;
FIG. 2 shows Fe obtained in comparative example of the present invention3O4SEM images of nanomaterials;
FIG. 3 is an SEM image of the magnetic Fe-Mn oxide nanomaterial prepared in example 2 of the present invention;
FIG. 4 is a mapping chart of the magnetic Fe-Mn oxide nanomaterial prepared in example 2 of the present invention;
FIG. 5 is an energy spectrum of the magnetic Fe-Mn oxide nanomaterial prepared in example 2 of the present invention;
FIG. 6 shows Pb obtained in application example 1 of the present invention2+The removal rate curve of (2);
FIG. 7 shows Pb obtained in application example 2 of the present invention2+The removal rate curve of (2);
FIG. 8 shows Zn obtained in application example 2 of the present invention2+The removal rate curve of (1).
Detailed Description
The purpose, technical scheme and advantages of the present application are further described below with reference to the accompanying drawings and embodiments, so that the present application is more clearly described. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Comparative example
Preparing a magnetic iron-based manganese oxide nano material:
(1) dissolving 0.46 urea in a mixed solution of 6mL of absolute ethyl alcohol and 0.5mL of hydrochloric acid (12mol/L), and stirring at room temperature until the urea is completely dissolved;
(2) 0.5964g of FeCl were added to the above solution2·4H2O, stirring for 15 min;
(3) adding 25mL of ethylene glycol after the step (2), and continuing stirring for 15 min;
(4) pouring the solution obtained in the step (3) into a high-pressure reaction kettle, and reacting for 5 hours at a constant temperature of 170 ℃;
(5) cooling the solution reacted in the step (4) along with a furnace, centrifugally separating, washing, and drying at 80 ℃ until the moisture is completely volatilized to obtain Fe3O4。
According to the comparative example, the product was analyzed by X-ray diffraction, the X-ray diffraction of which is shown in FIG. 1: a) as shown. Analytically determined phase as Fe3O4(ii) a Scanning electron microscopy is shown in FIG. 2.
Example 1
Preparing a magnetic iron-based manganese oxide nano material:
(1) dissolving 0.46 urea in a mixed solution of 6mL of absolute ethyl alcohol and 0.5mL of hydrochloric acid (12mol/L), and stirring at room temperature until the urea is completely dissolved;
(2) 0.5964g of FeCl were added to the above solution2·4H2O, stirring for 15 min;
(3) adding 25mL of ethylene glycol after the step (2), and continuing stirring for 15 min;
(4) pouring the solution obtained in the step (3) into a high-pressure reaction kettle, and reacting for 5 hours at a constant temperature of 170 ℃;
(5) cooling the solution reacted in the step (4) along with a furnace, centrifugally separating, washing, and drying at 80 ℃ until the moisture is completely volatilized to obtain Fe3O4；
(6) Drying the Fe obtained in the step (5)3O4Soaking in 0.05mol/L potassium permanganate solution for 0.5h, centrifugally separating, washing, and vacuum drying at 70 ℃ until the water is completely volatilized to obtain the magnetic iron-based-manganese oxide nano material.
According to example 1, the X-ray diffraction is as in figure 1: b) analysis determined whether the phase was Fe3O4+γ﹣Fe2O3+Mn3O4。
Example 2
Preparing a magnetic iron-based manganese oxide nano material:
(1) dissolving 0.46 urea in a mixed solution of 6mL of absolute ethyl alcohol and 0.5mL of hydrochloric acid (12mol/L), and stirring at room temperature until the urea is completely dissolved;
(2) 0.5964g of FeCl were added to the above solution2·4H2O, stirring for 15 min;
(3) adding 25mL of ethylene glycol after the step (2), and continuing stirring for 15 min;
(4) pouring the solution obtained in the step (3) into a high-pressure reaction kettle, and reacting for 5 hours at a constant temperature of 170 ℃;
(5) cooling the solution reacted in the step (4) along with a furnace, centrifugally separating, washing, and drying at 80 ℃ until the moisture is completely volatilized to obtain Fe3O4；
(6) Drying the Fe obtained in the step (5)3O4Soaking in 0.1mol/L potassium permanganate solution for 0.5h, centrifugally separating, washing, and vacuum drying at 80 ℃ until the water is completely volatilized to obtain the magnetic iron-based-manganese oxide nano material.
According to example 2, the X-ray diffraction is as in figure 1: c) as shown in the drawings, the above-described,analytically determined phase as Fe3O4+γ﹣Fe2O3+Mn3O4(ii) a The scanning electron microscope is shown in FIG. 3, and FIGS. 4 and 5 are mapping and energy spectrum diagrams of example 2.
Example 3
Preparing a magnetic iron-based manganese oxide nano material:
(1) dissolving 0.46 urea in a mixed solution of 6mL of absolute ethyl alcohol and 0.5mL of hydrochloric acid (12mol/L), and stirring at room temperature until the urea is completely dissolved;
(2) 0.5964g of FeCl were added to the above solution2·4H2O, stirring for 15 min;
(3) adding 25mL of ethylene glycol after the step (2), and continuing stirring for 15 min;
(4) pouring the solution obtained in the step (3) into a high-pressure reaction kettle, and reacting for 5 hours at a constant temperature of 170 ℃;
(5) cooling the solution reacted in the step (4) along with a furnace, centrifugally separating, washing, and drying at 80 ℃ until the moisture is completely volatilized to obtain Fe3O4；
(6) Drying the Fe obtained in the step (5)3O4Soaking in 0.2mol/L potassium permanganate solution for 0.5h, centrifugally separating, washing, and vacuum drying at 70 ℃ until the water is completely volatilized to obtain the magnetic iron-based-manganese oxide nano material.
According to example 3, the X-ray diffraction is as in FIG. 1: d) shown, the phase was analytically determined to be Fe3O4+γ﹣Fe2O3+Mn3O4。
Application example 1
Fe obtained in comparative example3O4The nanometer material and the magnetic iron-based-manganese oxide nanometer material prepared in the embodiments 1-3 are respectively used for removing heavy metal ions, and the method specifically comprises the following steps:
(1) preparation of 10 mg. L-1Pb of2+Solution (lead nitrate) and divided into 4 portions of the same;
(2) fe obtained in comparative example3O4Nanomaterials and materials prepared in examples 1 to 3Magnetic Fe-based-Mn oxide nano-material is respectively put into the 4 parts of solution, and the concentration of the added nano-material is controlled to be 0.4 g.L-1Stirring;
(3) sampling at different times, centrifuging, collecting supernatant, and measuring Pb in the supernatant with atomic absorption spectrometer2+Concentration, calculating Pb at different times2+And (4) removing rate.
Application example 2
The magnetic iron-based manganese oxide nano material obtained in the embodiment 2 is used for removing heavy metal ions, and the method comprises the following specific steps:
(1) simulating and preparing lead-zinc tailing industrial wastewater:
10 mg·L-1pb of2+Solutions (lead nitrate); 40 mg. L-1Zn of (2)2+Solutions (zinc nitrate); 11.8 mg. L-1Mg of (2)2 +Solution (magnesium chloride); 34.4 mg. L-1Ca of (2)2+Solutions (calcium nitrate); 68.3 mg. L-1Na of (2)2+Solution (sodium sulfate); 6.44 mg. L-1K of+Solution (potassium chloride);
(2) the prepared magnetic iron-based-manganese oxide nano material is put into the solution, and the concentration of the put nano material is controlled to be 0.4 g.L-1Stirring;
(3) sampling at different times, centrifuging, collecting supernatant, and measuring Pb in the supernatant with atomic absorption spectrometer2+、Zn2+Concentration, calculating Pb at different times2+、Zn2+And (4) removing rate.
From the data of application example 1 above, Pb as shown in FIG. 6 was obtained2+The removal rate curve of (1). From the data of application example 2 above, Pb as shown in FIG. 7 was obtained2+Removal rate curve of (1), Zn shown in FIG. 82+Removal rate curve.
As can be seen from FIG. 6, comparative group Fe3O4For Pb2+The effect is poor due to the adsorption; but passed through different concentrations of KMnO4Solution treated Fe3O4The effect is obviously improved; the concentration of potassium permanganate is 0.05mol/L and 0.1moL/L, 0.2mol/L, the adsorption performance of the sample is increased along with the increase of the concentration, and Pb can be adsorbed within 1min2+Adsorbing to below 1ppm to reach the discharge standard; however, after 0.1mol/L, the performance is not obviously improved, and in view of the raw material cost, the KMnO of 0.1mol/L is used in the experiment4Taking the concentration as a sample, and carrying out subsequent experiments.
According to the data of the above application example 2, our sample was applied to Pb in industrial wastewater of lead-zinc tailings2+、Zn2+As can be seen from fig. 7 and 8, the sample of the experiment also shows Pb-tolerant in the industrial wastewater of lead-zinc tailings2+Good adsorption effect, and can adsorb Pb in 5min2+Adsorbing to below 1ppm to reach the discharge standard; also shows good response to Pb2+Selective adsorption of (3).
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (2)
1. A method for preparing nano magnetic iron-manganese oxide is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving urea in a mixed solution of absolute ethyl alcohol and hydrochloric acid, and stirring at room temperature until the urea is completely dissolved;
(2) adding a ferrous iron source into the solution obtained in the step (1), and continuously stirring;
(3) adding ethylene glycol into the solution obtained in the step (2), and then continuing stirring;
(4) pouring the solution obtained in the step (3) into a high-pressure reaction kettle for constant-temperature reaction;
(5) cooling the solution reacted in the step (4) along with a furnace, and performing centrifugal separation, washing and drying until the water is completely volatilized to obtain Fe3O4；
(6) Drying the Fe obtained in the step (5)3O4Is placed in KMnO4Soaking the solution for 0.5h, centrifugally separating, washing and drying in vacuum until the water is completely volatilized to obtain the magnetic iron-based-manganese oxide nano material;
in the mixed solution of the absolute ethyl alcohol and the hydrochloric acid in the step (1), the volume ratio of the absolute ethyl alcohol to the hydrochloric acid is 12: 1; the constant-temperature reaction in the step (4) is specifically as follows: reacting for 2-6 h at constant temperature of 160-180 ℃;
the ferrous iron source in the step (2) is FeCl2·4H2O, the concentration is 0.1-1.0 mol/L;
in the step (6), the KMnO4The concentration of the solution is 0.005-0.4mol/L, and the vacuum drying temperature is 60-80 ℃.
2. The method of claim 1, wherein the method comprises the steps of: the drying temperature in the step (5) is 70-90 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102068995A (en) * | 2011-01-11 | 2011-05-25 | 河北师范大学 | Preparation method of nano magnetic core-shell catalyst for degrading dye wastewater |
| CN102172510A (en) * | 2011-04-01 | 2011-09-07 | 哈尔滨工业大学 | Preparation method of MnO2/Fe3O4 compound adsorbent and method for removing lead in water with compound adsorbent |
| CN105688793A (en) * | 2016-01-25 | 2016-06-22 | 华东交通大学 | Preparation method of MnO2-based magnetic nano Fe3O4 heavy metal adsorbing material |
| CN105771934A (en) * | 2016-05-06 | 2016-07-20 | 扬州大学 | Preparation method of nanometer magnetic adsorbent with core-shell structure |
| CN105771877A (en) * | 2016-04-23 | 2016-07-20 | 上海大学 | Method for preparing composite adsorption material MnO2-Fe3O4 with core-shell structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102068995A (en) * | 2011-01-11 | 2011-05-25 | 河北师范大学 | Preparation method of nano magnetic core-shell catalyst for degrading dye wastewater |
| CN102172510A (en) * | 2011-04-01 | 2011-09-07 | 哈尔滨工业大学 | Preparation method of MnO2/Fe3O4 compound adsorbent and method for removing lead in water with compound adsorbent |
| CN105688793A (en) * | 2016-01-25 | 2016-06-22 | 华东交通大学 | Preparation method of MnO2-based magnetic nano Fe3O4 heavy metal adsorbing material |
| CN105771877A (en) * | 2016-04-23 | 2016-07-20 | 上海大学 | Method for preparing composite adsorption material MnO2-Fe3O4 with core-shell structure |
| CN105771934A (en) * | 2016-05-06 | 2016-07-20 | 扬州大学 | Preparation method of nanometer magnetic adsorbent with core-shell structure |
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