CN114149068A - Perovskite type composite oxide containing high-valence iron Fe (IV), and low-temperature roasting synthesis method and application thereof - Google Patents

Perovskite type composite oxide containing high-valence iron Fe (IV), and low-temperature roasting synthesis method and application thereof Download PDF

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CN114149068A
CN114149068A CN202111396207.1A CN202111396207A CN114149068A CN 114149068 A CN114149068 A CN 114149068A CN 202111396207 A CN202111396207 A CN 202111396207A CN 114149068 A CN114149068 A CN 114149068A
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张其武
胡慧敏
陈敏
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Wuhan University of Technology WUT
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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
    • 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
    • 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
    • C02F2101/103—Arsenic compounds
    • 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
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols
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    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract

The invention relates to a perovskite type composite oxide containing high-valence iron Fe (IV), a low-temperature roasting synthesis method and application thereof1‑xFexO3M is Mn or Ti, x is more than or equal to 0.3 and less than or equal to 0.7. The perovskite type composite oxide provided by the invention has high content of high-valence iron Fe (IV), so that the perovskite type composite oxide has excellent oxidation performance, has a degradation rate of degrading typical organic and inorganic pollutants of more than 98 percent, has good economic value, is green, environment-friendly and pollution-free in the preparation method, mild in roasting condition (low in roasting temperature and short in roasting time), and is beneficial to industryAnd (5) large-scale production.

Description

Perovskite type composite oxide containing high-valence iron Fe (IV), and low-temperature roasting synthesis method and application thereof
Technical Field
The invention belongs to the technical field of catalysts containing iron-based metals, and particularly relates to a perovskite-type composite oxide containing high-valence iron Fe (IV), and a low-temperature roasting synthesis method and application thereof.
Background
Ferrate is a new high-efficiency nontoxic multifunctional water treatment agent which is concerned. The current high-valence iron oxide is mainly potassium ferrate (K)2FeO4) Mainly, chlorine and sodium hydroxide react to generate saturated sodium hypochlorite concentrated alkali liquor, ferric nitrate is used for oxidation, and potassium hydroxide is used for dissolution to obtain the sodium hypochlorite concentrated alkali liquor; or electrolyzing ferric trichloride and sodium hydroxide solution, and reacting with potassium hydroxide to obtain the final product. As the prior preparation process is not mature and the process is complicated, the potassium ferrate is supplied in the market less till now. In addition, potassium ferrate powder is stable only in dry air below 198 deg.c, is easy to absorb water at normal temperature, is very easy to dissolve in water to form light purple red solution, and may decompose to release oxygen after being set in air to produce hydrated iron oxide and thus lose its oxidation performance. The overall use of ferrate (VI) in the water and wastewater industries is not yet mature.
Researchers found that the intermediate iron species Fe (IV)/Fe (V) plays an important role in the oxidation of potassium ferrate, and reported that the reactivity of Fe (IV)/Fe (V) is much higher than that of Fe (VI). The intermediate state Fe (IV)/Fe (V) in the solution is difficult to maintain for a long time, so that the synthesis of a stable solid oxidant containing Fe (IV) is worthy of being searched, and the problem that the stability of the high-valence iron salt is poor and the industrial application is difficult to realize can be solved.
The traditional method for synthesizing the perovskite material containing quadrivalent iron is very difficult, and the stable oxide containing Fe (IV) is reported to be CaFeO3As a representative, the CaFeO reported earlier3The high-temperature solid-phase synthesis process needs harsh conditions, roasting is required to be carried out in an oxygen-enriched environment with the temperature of 1100 ℃, the roasting time is as long as 24 hours, partial researchers can adjust and use a coprecipitation method, a sol-gel method and the like to reduce the roasting temperature, but the similar liquid-phase process is complex, most raw materials are metal salts, waste liquid and waste gas with high salt content are generated in the synthesis process, and synthesized samples contain partial residues of organic matters and salts.
Based on the above background, the present invention proposes to introduce Mn, Ti element capable of existing in tetravalent state stably, and use it to form perovskite crystal structure (CaMnO) with stable structure3,CaTiO3) In the air, the CaM containing Fe (IV) is synthesized by low-temperature roasting1-xFexO3(M:Mnthe/Ti) perovskite type oxide is expected to be widely applied in the field of catalytic degradation of organic and inorganic pollutants in water.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides a high-valence Fe (IV) composite oxide, a preparation method and application thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
provides a perovskite type composite oxide containing high-valence iron Fe (IV), the perovskite type composite oxide containing high-valence iron Fe (IV) has a stable perovskite crystal structure, and the chemical structural formula is CaM1-xFexO3M is Mn or Ti, x is more than or equal to 0.3 and less than or equal to 0.7.
The invention also provides a low-temperature roasting synthesis method of the perovskite type composite oxide containing high-valence iron Fe (IV), which comprises the following specific steps:
3) preparing a precursor: according to CaM1-xFexO3Weighing a calcium source, an M source and an iron source according to a stoichiometric ratio, mixing, ball-milling and activating to obtain a precursor sample;
4) preparing high-valence Fe (IV) composite oxide by low-temperature roasting: roasting the precursor sample obtained in the step 1) in an air atmosphere, wherein the roasting conditions are as follows: heating to 700-900 ℃ at the speed of 5-10 ℃/min at room temperature, preserving heat for 2.5-5 h, and naturally cooling to room temperature to obtain CaM1-xFexO3An oxide.
According to the scheme, the calcium source in the step 1) is CaO or Ca (OH)2(ii) a The M source is MnO2Or TiO2(ii) a The iron source is FeOOH.
According to the scheme, the calcium source, the M source and the iron source are analytically pure, and the particle size is less than 100 meshes.
According to the scheme, the ball milling activation process conditions in the step 1) are as follows: ball milling is carried out for 1-4 h at the rotating speed of 600-800 rpm.
The invention also comprises the application of the perovskite type composite oxide containing high-valence iron Fe (IV) in the aspect of oxidizing and degrading organic and inorganic pollutants in water, and the specific use method is as follows: adding the perovskite type composite oxide containing high-valence iron Fe (IV) into a water body containing target pollutants, and continuously stirring for 30-360 min under the air atmosphere at normal temperature and normal pressure, so that the pollutants can be subjected to oxidative degradation.
According to the scheme, the target pollutants comprise As (III) compounds, phenol and acid violet 43.
According to the scheme, the addition amount of the perovskite type composite oxide containing high-valence iron Fe (IV) in the water body is 0.5-2 g/L.
The reaction process for synthesizing the perovskite type composite oxide containing high-valence iron Fe (IV) comprises the following steps:
Figure BDA0003370429860000031
in the ball milling activation process of the raw materials, the raw materials are continuously crushed, sheared and extruded by a ball milling medium, the amorphous degree of the original phase is increased, the mixing degree among the materials is enhanced, the rearrangement of atoms is more facilitated, and the mixed precursor sample is favorable for the recrystallization process in the later roasting process. The applicant finds that a ball-milling preactivated sample is more beneficial to reducing the subsequent roasting temperature of the material and is simultaneously compared with CaFeO3Synthesis of (2), MnO2Or TiO2The addition of the tetravalent oxide is beneficial to the construction of a perovskite structure, and the harsh conditions of oxygen enrichment and high pressure in the process of synthesizing the oxide containing the tetravalent iron perovskite by the traditional solid phase method are avoided.
The invention has the beneficial effects that: 1. the perovskite type composite oxide provided by the invention has high content of high valence iron Fe (IV) (the proportion of tetravalent iron Fe in B position can be up to 70%), so that the perovskite type composite oxide has excellent oxidation performance, the degradation rate of typical organic and inorganic pollutants can be up to more than 98%, and the perovskite type composite oxide has good economic value. 2. The preparation method disclosed by the invention has the advantages that the whole synthesis process is an all-solid-phase reaction, no organic matter and acid-base are used, no other impurity ions are introduced, no waste water and waste gas are discharged, the preparation method is green, environment-friendly and pollution-free, the roasting condition is mild (the roasting temperature is low, the roasting time is short), the industrial large-scale production is facilitated, and great economic benefits are realized.
Drawings
FIG. 1 shows the CaMn containing high valence Fe-perovskite structure obtained in example 1 of the present invention1-xFexO3XRD pattern of oxide;
FIG. 2 shows the perovskite structure CaTi containing high valence Fe-Ca prepared in example 21-xFexO3XRD pattern of oxide;
FIG. 3 is a graph showing the effect of the application example 1 in oxidizing and removing As (III);
FIG. 4 is a graph showing the effect of application example 2 in oxidizing and degrading phenol by using iron oxide with high valence;
FIG. 5 is a graph showing the effect of the application example 3 in the oxidative degradation of acid violet 43 by using iron oxide with high valence.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention is further described in detail below with reference to the accompanying drawings.
Example 1
Preparation of high-valence Fe (IV) composite oxide CaMn1-xFexO3And x is 0.3, 0.5 and 0.7, and the specific steps are as follows:
1) according to the mol ratio of 1: 1-x: weighing calcium source (CaO, analytically pure, below 100 meshes) and Mn source (MnO) according to the proportion of x2) Placing the raw materials on a planetary ball mill for ball milling activation, wherein the ball milling rotation speed is 700rpm, and the ball milling time is 2 hours to obtain a precursor sample;
2) roasting the obtained precursor sample in an air atmosphere, wherein the roasting conditions are as follows: heating to 700 deg.C at a rate of 10 deg.C/min at room temperature, maintaining for 2.5h, and naturally cooling to room temperature to obtain pure black powder CaMn1-xFexO3。
CaMn prepared in this example1-xFexO3The XRD test pattern is shown in figure 1, and the XRD result in figure 1 shows that when x is 0.3-0.7Can synthesize CaMn containing high-valence iron1-xFexO3The XRD diffraction pattern of the perovskite sample and the synthesized sample is consistent with the standard pattern without the generation of other impurity phases, and the XRD diffraction peak of the sample shifts to a high angle along with the reduction of x, which indicates that Fe can replace Mn in a lattice structure to participate in the synthesis of the perovskite material as B-site element, and simultaneously confirms that Fe exists in quadrivalence.
Example 2
Preparation of high-valence Fe (IV) composite oxide CaTi1-xFexO3And x is 0.3, 0.5 and 0.7, and the specific steps are as follows:
1) according to the mol ratio of 1: 1-x: weighing calcium source (CaO, analytically pure, below 100 meshes) and Ti source (TiO) according to the proportion of x2) Placing the raw materials on a planetary ball mill for ball milling activation, wherein the ball milling rotation speed is 700rpm, and the ball milling time is 2 hours to obtain a precursor sample;
2) roasting the obtained precursor sample in an air atmosphere, wherein the roasting conditions are as follows: heating to 700 deg.C at a rate of 10 deg.C/min at room temperature, maintaining for 2.5h, and naturally cooling to room temperature to obtain pure black powder CaMn1-xFexO3。
CaTi prepared in this example1-xFexO3The XRD test pattern is shown in FIG. 2, and it can be known from the XRD result in FIG. 2 that when the value of x is 0.3. ltoreq. x.ltoreq.0.7, CaTi containing high valence iron can be synthesized1-xFexO3The XRD diffraction pattern of the perovskite sample and the synthetic sample is consistent with the standard pattern, and no other impurity phase is generated.
Application example 1
CaMn containing high-valence iron prepared in example 1 of the invention0.3Fe0.7O3The application of the perovskite sample in the aspect of removing As (III) pollutants in wastewater by oxidation comprises the following specific steps:
1) preparing a simulated sewage sample: adding NaAsO2Dissolving in ultrapure water, and preparing an As (III) solution with the concentration of 20 mg/L;
2) CaMn prepared in example 1 was added to a simulated wastewater sample0.3Fe0.7O3Powder with the addition of 1g/L is stirred and reacted for 360min, and the oxidation and the removal of As (III) in the sewage are completed.
As (III) removal effect is shown in FIG. 3, the total arsenic concentration and the trivalent arsenic concentration in the solution are gradually reduced along with the progress of the reaction, the trivalent arsenic concentration in the solution is only 0.07mg/L after 360min of the reaction, and the removal rate of the trivalent arsenic reaches 99.6%. As shown by the valence distribution of arsenic in the residue after the reaction, 86.4 percent of arsenic in the residue is pentavalent arsenic, which indicates that CaMn0.3Fe0.7O3Has the capability of oxidizing trivalent arsenic which is a typical inorganic pollutant.
Application example 2
CaMn containing high-valence iron prepared in example 1 of the invention0.7Fe0.3O3The application of the perovskite sample in the aspect of removing phenol pollutants in wastewater by oxidation comprises the following specific steps:
1) preparing a simulated sewage sample: 10mg/L of phenol solution;
2) CaMn prepared in example 1 was added to a simulated wastewater sample0.7Fe0.3O3And (3) adding 1g/L of powder, and stirring to react for 360min to complete the oxidative degradation of phenol in the sewage.
The effect graph of oxidative degradation of phenol is shown in fig. 4, along with the reaction, the solubility of phenol in the solution at the early stage is sharply reduced, the solution gradually tends to be stable after the reaction is carried out for 240min, the removal rate of phenol is 100% after the reaction is finished, and the phenol is completely removed by oxidative degradation, thereby confirming that CaMn is removed0.7Fe0.3O3The material has excellent oxidation performance.
Application example 3
CaTi containing high-valence iron prepared in example 2 of the invention0.3Fe0.7O3The application of the perovskite sample in the aspect of removing acid violet 43 pollutants in wastewater by oxidation comprises the following specific steps:
1) preparing a simulated sewage sample: 20mg/L acid violet 43 solution;
2) CaTi prepared in example 2 was added to a simulated wastewater sample0.3Fe0.7O3Adding powder in an amount of 1g/L, and stirring for reactionAnd (4) finishing the oxidative decoloration degradation of the acid violet 43 in the sewage in 360 min.
The effect graph of oxidative degradation of acid violet 43 is shown in fig. 5, the concentration of acid violet 43 in the solution gradually decreases with the progress of the reaction, the solution is nearly completely degraded and decolorized at 240min, the removal rate of acid violet 43 reaches 99.4% after 360min of reaction, the purple color basically disappears, and the fact that the CaCI0.3Fe0.7O3The material has excellent oxidation performance.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (8)

1. The perovskite type composite oxide containing high-valence iron Fe (IV) is characterized by having a stable perovskite crystal structure and having a chemical structural formula of CaM1-xFexO3M is Mn or Ti, x is more than or equal to 0.3 and less than or equal to 0.7.
2. The low-temperature roasting synthesis method of the perovskite type composite oxide containing high-valence iron Fe (IV) according to claim 1, which is characterized by comprising the following specific steps:
1) preparing a precursor: according to CaM1-xFexO3Weighing a calcium source, an M source and an iron source according to a stoichiometric ratio, mixing, ball-milling and activating to obtain a precursor sample;
2) preparing high-valence Fe (IV) composite oxide by low-temperature roasting: roasting the precursor sample obtained in the step 1) in an air atmosphere, wherein the roasting conditions are as follows: heating to 700-900 ℃ at the speed of 5-10 ℃/min at room temperature, preserving heat for 2.5-5 h, and naturally cooling to room temperature to obtain CaM1-xFexO3An oxide.
3. The low-temperature calcination synthesis method of perovskite-type composite oxide containing high-valence iron Fe (IV) according to claim 2, wherein the calcium source in step 1) is CaO or Ca (OH)2(ii) a The M source is MnO2Or TiO2(ii) a The iron source is FeOOH.
4. The method for synthesizing a perovskite-type composite oxide containing high-valence iron Fe (IV) according to claim 3, wherein the calcium source, the M source and the iron source are analytically pure and have a particle size of 100 mesh or less.
5. The low-temperature roasting synthesis method of perovskite type composite oxide containing high-valence iron Fe (IV) according to claim 2, characterized in that the ball milling activation process conditions in step 1) are as follows: ball milling is carried out for 1-4 h at the rotating speed of 600-800 rpm.
6. The application of the perovskite-type composite oxide containing high-valence iron Fe (IV) in the claim 1 in the aspect of oxidizing and degrading organic and inorganic pollutants in a water body is characterized in that the specific use method is as follows: adding the perovskite type composite oxide containing high-valence iron Fe (IV) into a water body containing target pollutants, and continuously stirring for 30-360 min under the air atmosphere at normal temperature and normal pressure, so that the pollutants can be subjected to oxidative degradation.
7. The use of the perovskite-type composite oxide containing high-valence iron Fe (IV) according to claim 6 for the oxidative degradation of organic and inorganic pollutants in a water body, wherein the target pollutants comprise As (III) compounds, phenol and acid violet 43.
8. The application of the perovskite-type composite oxide containing high-valence iron Fe (IV) in the aspect of oxidizing and degrading organic and inorganic pollutants in a water body according to claim 6, wherein the addition amount of the perovskite-type composite oxide containing high-valence iron Fe (IV) in the water body is 0.5-2 g/L.
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Citations (4)

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Publication number Priority date Publication date Assignee Title
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CN110723803A (en) * 2019-10-22 2020-01-24 哈尔滨工业大学 Method for removing pollutants in water by using high-valence ferric salt composite reagent
CN111871422A (en) * 2020-07-21 2020-11-03 上海交通大学 Application of calcium-manganese oxide catalyst in degradation of organic pollutants in wastewater and soil

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1933331A1 (en) * 1968-07-02 1970-01-29 Commissariat Energie Atomique Process for the production of homogeneous oxides of several elements in finely divided form and products obtained
CN1203831A (en) * 1998-05-06 1999-01-06 南京化工大学 Mixed conductive compact oxygen permeable membrane material
CN110723803A (en) * 2019-10-22 2020-01-24 哈尔滨工业大学 Method for removing pollutants in water by using high-valence ferric salt composite reagent
CN111871422A (en) * 2020-07-21 2020-11-03 上海交通大学 Application of calcium-manganese oxide catalyst in degradation of organic pollutants in wastewater and soil

Non-Patent Citations (1)

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Title
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