CN114425348A - Nano composite oxide and preparation method and application thereof - Google Patents

Nano composite oxide and preparation method and application thereof Download PDF

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CN114425348A
CN114425348A CN202011015674.0A CN202011015674A CN114425348A CN 114425348 A CN114425348 A CN 114425348A CN 202011015674 A CN202011015674 A CN 202011015674A CN 114425348 A CN114425348 A CN 114425348A
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precursor
oxide
nanocomposite
nano composite
heating
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CN114425348B (en
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杨晏泉
孙杰
曹宗仑
龚小芝
常田
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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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
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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    • C—CHEMISTRY; METALLURGY
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Abstract

The invention relates to the field of water treatment, and discloses a nano composite oxide, a preparation method and application thereof, wherein the method comprises the following steps: mixing an iron precursor, a cobalt precursor, a dispersion medium, a template agent and a complexing agent for a complexing reaction, and then drying and roasting the mixture in sequence to obtain the nano composite oxide. The method is simple and convenient, easy to operate, low in raw material cost, low in roasting temperature, good in shape uniformity of the obtained nano composite oxide and easy for large-scale production and application.

Description

Nano composite oxide and preparation method and application thereof
Technical Field
The invention relates to the field of water treatment, in particular to a nano composite oxide and a preparation method and application thereof.
Background
The petrochemical wastewater has complex components, high COD content, large water quality fluctuation, poor biodegradability, more refractory substances such as hydrocarbons and derivatives thereof, and great difficulty in treatment and recycling. Along with the continuous increase of the processing depth of crude oil, the standard treatment difficulty of petrochemical sewage by the traditional biochemical method is increased day by day, and the organic matters which are difficult to degrade form a larger pollution risk to the environment. With the increasing strictness of environmental requirements, the emission standards of pollutants in the petroleum refining industry (GB 31570-2015) and pollutants in the petrochemical industry (GB 31571-2015) both stipulate that the COD emission concentration of the total wastewater discharge port of an enterprise does not exceed 60mg/L, and a stricter 50mg/L special emission limit value is implemented in a special area. Therefore, the efficient advanced treatment technology of sewage is urgently needed to be developed and applied.
Since the 80 s of the 20 th century, a series of advanced oxidation technologies (AOPs) were developed and developed, which mainly utilize physical or chemical processes to generate hydroxyl radicals (OH) as an intermediate with high activity to oxidize and decompose organic substances in sewage into CO2Or a small molecule compound. The hydroxyl free radical has the characteristics of strong oxidizing property and no selectivity, can oxidize or mineralize most organic pollutants, and does not cause secondary pollution. The advanced oxidation technology has the characteristics of wide application range, high reaction rate and strong oxidation capability, and has remarkable advantages in the aspect of treating high-toxicity and difficultly-degraded wastewater. The catalytic ozonation technology is one of the mainstream advanced oxidation technologies, utilizes ozone to generate a large amount of hydroxyl radicals in water under the action of a catalyst, has high reaction speed, mild conditions and no secondary pollution, and can be widely applied to the field of sewage treatment.
The catalytic oxidation technology of ozoneThe bond is the development of catalysts, which fall into two broad categories, homogeneous and heterogeneous. Homogeneous catalysts are costly and difficult to recover, and therefore have limited application areas. Heterogeneous catalysts are the focus of research and application, and are classified into supported catalysts and unsupported catalysts. The supported catalyst is prepared by loading active components (generally noble metal or monobasic oxide) on active carbon, molecular sieve and gamma-Al2O3On the carrier, the main defects are as follows: (1) the number of active sites is small, and active components are easy to agglomerate, so that the activity of the catalyst is low; (2) the specific surface area is small, and the contact area of the active point position and the reactant is insufficient; (3) the binding force between the active component and the carrier is weaker, the active component is easy to lose, the pollution is caused, and the service life of the catalyst is shortened.
The metal oxide is an important ozone catalytic oxidation catalyst, and at present, when the nano composite oxide is prepared by the traditional preparation method, the particle size of the product is larger and the particle size distribution is not uniform. Therefore, the preparation and application of the composite oxide ozone catalytic oxidation catalyst are greatly limited.
Therefore, the existing ozone catalytic oxidation technology needs to be further improved.
Disclosure of Invention
The invention aims to overcome the technical problems of higher catalyst cost, more difficult recovery, small specific surface area, less active sites, easy agglomeration of active components, easy loss of the active components, lower catalytic activity, larger product particle size and nonuniform particle size distribution in the prior art, and provides a nano composite oxide, a preparation method and application thereof.
In order to achieve the above object, according to a first aspect of the present invention, there is provided a method for preparing a nanocomposite oxide, the method comprising: mixing an iron precursor, a cobalt precursor, an optional chromium precursor, a dispersion medium, a template agent and a complexing agent for a complexing reaction, and then drying and roasting the mixture in sequence to obtain the nano composite oxide.
The method for preparing the nano composite oxide provided by the invention has the advantages that the product obtained by the method has small particle size and uniform particle size distribution, the preparation process is simple and convenient, the operation is easy, the raw material cost is low, the obtained nano composite oxide has good shape uniformity, and the large-scale production and application are easy.
In a second aspect of the present invention, there is provided a nanocomposite oxide, which is prepared by the above method.
In a third aspect of the present invention, there is provided a method of wastewater treatment, the method comprising: in the presence of ozone, the sewage is contacted with the nano composite oxide to carry out catalytic reaction;
or preparing the nano composite oxide according to the method, and then contacting the sewage with the obtained nano composite oxide in the presence of ozone to perform catalytic reaction.
According to the method for treating the sewage, the sewage is contacted with the nano composite oxide in the presence of ozone to carry out catalytic reaction so as to remove organic matters in the sewage, and the nano composite oxide has the advantages of large specific surface area, multiple surface active sites and the like, so that the organic matters in the sewage can be effectively removed, the COD (chemical oxygen demand) concentration in the sewage is reduced, and in addition, the nano composite oxide has greater advantages in the aspect of catalytic activity than a single metal oxide.
In the fourth aspect of the invention, the nano composite oxide prepared by the method and the application of the nano composite oxide in water treatment are provided.
A fifth aspect of the present invention provides a nanocomposite oxide comprising Fe, Co and optionally Cr, wherein the nanocomposite oxide has an XRD pattern with characteristic peaks at 2 θ of 18.4 ± 0.2 °, 30.3 ± 0.2 °, 35.7 ± 0.2 °, 37.3 ± 0.2 °, 43.4 ± 0.2 °, 53.8 ± 0.2 °, 57.4 ± 0.2 °, 63 ± 0.2 ° and 90.4 ± 0.2 °.
The nano composite oxide provided by the invention is spinel type ferrite, has a plurality of oxygen vacancies and good chemical stability, and the catalyst particle size is only about 100nm, and the specific surface area reaches 20m2The concentration of the ozone is 10-20 times of that of a common supported catalyst, so that the active area of the ozone catalyst is greatly increased, and the ozone catalyst can be effectively usedThe reaction efficiency of refractory organics in sewage is improved, and in addition, the surface active sites are widely and uniformly distributed, so that more hydroxyl free radicals are generated, the loss of active substances is reduced, and the metal pollution generated by the catalyst can be effectively reduced. And the nano composite oxide is easy to recover, the active components are not easy to agglomerate, the active components are not easy to lose, the catalytic activity is high, and the nano composite oxide is easy to produce and apply on a large scale.
Drawings
FIG. 1 is an X-ray diffraction diagram of a nanocomposite oxide obtained according to example 1;
fig. 2 is a transmission electron microscope image of the nanocomposite oxide obtained according to example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect of the present invention, there is provided a method for producing a nanocomposite oxide, the method comprising: mixing an iron precursor, a cobalt precursor, an optional chromium precursor, a dispersion medium, a template agent and a complexing agent for a complexing reaction, and then drying and roasting the mixture in sequence to obtain the nano composite oxide.
In some embodiments of the present invention, preferably, the average particle diameter of the nanocomposite oxide is 10 to 5000nm, more preferably 20 to 100 nm.
In some embodiments of the invention, the complexation reaction further comprises adding a chromium precursor to perform the complexation reaction. The molar ratio of the amounts of the iron precursor, the cobalt precursor, and the optional chromium precursor is preferably 1: 1-2: 0-2, more preferably 1: 1-1.25: 1-1.5.
In some embodiments of the present invention, the amount of the dispersion medium, the templating agent, and the complexing agent is such that the weight ratio of the dispersion medium, the templating agent, and the complexing agent is preferably from 1.5 to 2: 0.3-0.5: 1.
in some embodiments of the present invention, the iron precursor and the templating agent are used in amounts such that the weight ratio of the iron precursor to the templating agent is preferably from 0.5 to 1: 1.
in some embodiments of the invention, the method may further comprise: dissolving the iron precursor, the cobalt precursor, and the optional chromium precursor under acidic conditions.
In the present invention, preferably, the iron precursor, the cobalt precursor, and the optional chromium precursor are dissolved under acidic conditions under stirring. In the present invention, the stirring conditions are not limited as long as the precursors of the respective components can be dissolved.
In some embodiments of the present invention, it is preferred that acidic conditions are controlled using an acidic substance, which is nitric acid and/or hydrochloric acid.
In some embodiments of the present invention, the amount of the acidic substance in terms of hydrogen ions is preferably 0.00125 to 0.03mol based on 0.005mol of the cobalt precursor.
In some embodiments of the invention, the acidic substance is provided in the form of a solution having a weight fraction of preferably 65 to 68 wt.%.
In some embodiments of the invention, the temperature of the dissolution is preferably 70-90 ℃.
In some embodiments of the present invention, the iron precursor is preferably a water-soluble iron salt, more preferably at least one selected from the group consisting of ferric nitrate, ferric chloride and ferric acetate.
In some embodiments of the present invention, the cobalt precursor is preferably a water-soluble cobalt salt, more preferably at least one selected from the group consisting of cobalt nitrate, cobalt chloride and cobalt acetate.
In some embodiments of the present invention, the optional chromium precursor is preferably a water-soluble chromium salt, more preferably at least one selected from the group consisting of chromium nitrate, chromium chloride and chromium acetate.
In some embodiments of the invention, the templating agent is preferably a nonionic surfactant; more preferably having the formula EOaPObEOaThe polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer of (a); further preferred, wherein a has a value of 10 to 100, b has a value of 40 to 80; EO is particularly preferred20PO70EO20。
In some embodiments of the present invention, to form a stable sol, the dispersion medium may be a monohydric alcohol of C2-C6, preferably n-butanol and/or n-pentanol.
In some embodiments of the invention, the complexing agent may be an organic acid, preferably citric acid.
In some embodiments of the invention, the time for the complexation reaction is preferably 24-48 h.
In some embodiments of the present invention, preferably, the iron precursor, the cobalt precursor, the optional chromium precursor, the dispersion medium, and the template are first contacted to obtain a first sol, and then the first sol is second contacted with the complexing agent to obtain a second sol. Specifically, the iron precursor, the cobalt precursor, the optional chromium precursor, the dispersion medium and the template agent are firstly contacted to form a first sol, and then the first sol is secondly contacted with the complexing agent to carry out a complexing reaction, so as to obtain a second sol with uniformly complexed metal ions.
In the present invention, the weight content of water in the first sol is 50 to 60% by weight.
In some embodiments of the present invention, preferably, the first contacting time is 12 to 24 hours. The time of the second contact is 12-24.
In some embodiments of the present invention, the drying conditions are not particularly limited, and the temperature increase rate of the drying is preferably 2 to 4 ℃/min. The temperature for drying is preferably 100-220 ℃. According to a preferred embodiment of the present invention, the drying is preferably performed by: heating to 100-120 deg.C at a heating rate of 2-4 deg.C/min, maintaining for 1-2h, heating to 150-180 deg.C, maintaining for 1-2h, heating to 220-240 deg.C, and maintaining for 5-6 h.
In some embodiments of the present invention, the conditions of the calcination are not particularly limited, and the temperature increase rate of the calcination is preferably 2 to 4 ℃/min. The temperature of the calcination is preferably 150 to 900 ℃. According to a preferred embodiment of the present invention, the firing is performed by: heating to 150-180 ℃ at a heating rate of 2-4 ℃/min, preserving heat for 10-12h, heating to 250-280 ℃, preserving heat for 2-3h, heating to 350-380 ℃, preserving heat for 1-2h, heating to 450-480 ℃, preserving heat for 1-2h, finally heating to 700-900 ℃, and preserving heat for 1-2 h; specifically, the temperature is naturally cooled to 20-40 ℃ between each heat preservation platform, and then the temperature is raised to the next heat preservation platform.
In a second aspect of the present invention, there is provided a nanocomposite oxide, which is prepared by the above method.
In a third aspect of the present invention, there is provided a method of wastewater treatment, the method comprising: in the presence of ozone, the sewage is contacted with the nano composite oxide to carry out catalytic reaction;
or preparing the nano composite oxide according to the method, and then contacting the sewage with the obtained nano composite oxide in the presence of ozone to perform catalytic reaction.
In the present invention, the catalytic reaction may be performed in a continuous flow reactor, and the type of the continuous flow reactor is not limited in the present invention, and may be a fixed bed reactor, a stacked bed reactor, a fluidized bed reactor, a moving bed reactor, or a bubbling bed reactor. In particular, the nanocomposite oxide may be arranged in layers in a continuous flow reactor (e.g., a fixed bed) or mixed with a reactant stream (e.g., an ebullating bed).
In some embodiments of the present invention, the amount of ozone is preferably 1.5 to 2.5m based on 1 ton of wastewater3。
In some embodiments of the invention, the temperature of the catalytic reaction is preferably in the range of 20 to 40 ℃. The time of the catalytic reaction is preferably 0.5 to 1 hour. The concentration of the ozone is preferably 30-40mg/L, and the flow rate is preferably 0.1-0.5L/min.
In the fourth aspect of the invention, the nano composite oxide prepared by the method and the application of the nano composite oxide in water treatment are provided.
A fifth aspect of the present invention provides a nanocomposite oxide comprising Fe, Co and optionally Cr, wherein the nanocomposite oxide has an XRD pattern with characteristic peaks at 2 θ of 18.4 ± 0.2 °, 30.3 ± 0.2 °, 35.7 ± 0.2 °, 37.3 ± 0.2 °, 43.4 ± 0.2 °, 53.8 ± 0.2 °, 57.4 ± 0.2 °, 63 ± 0.2 ° and 90.4 ± 0.2 °.
In some embodiments of the present invention, preferably, the nanocomposite oxide is spinel-type crystal, and the molar ratio of Fe, Co and Cr in the nanocomposite oxide is 1: 1-2: 0-2, more preferably 1: 1-1.25: 1-1.5. Specifically, the molecular formula of the nano composite oxide is FexCoyCrzO4Wherein x + y + z is 3.
In some embodiments of the present invention, the specific surface area, pore volume and pore diameter of the mesoporous catalyst can be measured according to a nitrogen adsorption method, the specific surface area is calculated by using a BET method, and the pore volume is calculated by using a BJH model. The specific surface area of the nanocomposite oxide is preferably 1 to 20m2A/g, more preferably 15 to 18m2(ii) in terms of/g. The pore volume of the nanocomposite oxide is preferably 0.0005 to 0.2cm3In terms of/g, more preferably 0.15 to 0.18cm3(ii) in terms of/g. The average pore diameter of the nanocomposite oxide is preferably 5 to 400nm, more preferably 230 to 380 nm. The average particle diameter of the nanocomposite oxide is preferably 10 to 5000nm, more preferably 20 to 100 nm.
In the invention, COD refers to Chemical Oxygen Demand (COD), the unit is mg/L, and the amount of reducing substances needing to be oxidized in a water sample is measured by a chemical method. The oxygen equivalent of a substance (typically an organic substance) that can be oxidized by a strong oxidizing agent in wastewater, wastewater treatment plant effluent, and contaminated water.
In the present invention, room temperature means 20 to 40 ℃.
In the invention, the sewage refers to biochemical effluent of a sewage treatment system of an refinery enterprise.
In the present invention, the pressure means a gauge pressure.
The present invention will be described in detail below by way of examples.
In the examples and comparative examples, the reagents used were all commercially available analytical reagents. The room temperature means "25 ℃. In the examples and comparative examples, the reagents used were all commercially available analytical reagents. Polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymers from J&K Scientific Ltd, trade name P123, molecular formula EO20PO70EO20And the molecular weight is 5800. Citric acid was purchased from west longa chemical gmbh. The sewage is the biochemical effluent of a sewage treatment system of a certain refinery enterprise, and the COD concentration of the sewage is 187 mg/L.
Example 1
(1) 0.005mol of Fe (NO)3)3·9H2O、0.005mol Co(NO3)2·6H2O and 0.005mol Cr (NO)3)3·9H2Adding O into 2g of concentrated nitric acid with the weight fraction of 65 weight percent, heating to 90 ℃, and stirring to completely dissolve the O;
(2) adding the mixed nitrate solution obtained in the step (1) into 14g of n-butanol, uniformly stirring, then adding 3g of P123 triblock copolymer, uniformly stirring, and continuously stirring for 24 hours at room temperature to obtain sol;
(3) adding 8g of citric acid monohydrate into the sol obtained in the step (2), and continuously stirring for 12 hours at room temperature to completely dissolve the citric acid monohydrate to obtain sol with metal ions uniformly complexed;
(4) placing the complex sol obtained in the step (3) in a drying oven, keeping the temperature at 120 ℃ for 2h, raising the temperature to 150 ℃ and keeping the temperature for 2h, and finally raising the temperature to 220 ℃ and keeping the temperature for 5h to obtain dry gel at the temperature rise rate of 2 ℃/min;
(5) and (4) placing the dried gel obtained in the step (4) in a muffle furnace, gradually increasing the roasting heat preservation temperature at the temperature rise rate of 2 ℃/min all the time, naturally cooling to 25 ℃ between each heat preservation platform, and then raising the temperature to the next heat preservation platform. The roasting heat preservation platform is sequentially used for preserving heat at 150 ℃ for 12 hours, preserving heat at 250 ℃ for 3 hours, preserving heat at 350 ℃ for 2 hours, preserving heat at 450 ℃ for 1 hour and preserving heat at 800 ℃ for 2 hours to obtain the nano composite oxide.
Example 2
(1) 0.004mol of Fe (NO)3)3·9H2O、0.005mol Co(NO3)2·6H2O and 0.006mol Cr (NO)3)3·9H2Adding O into 2g of concentrated nitric acid with the weight fraction of 68 percent and heated to 90 ℃, and stirring to completely dissolve the O;
(2) adding the mixed nitrate solution obtained in the step (1) into 14g of n-amyl alcohol, uniformly stirring, then adding 3g of P123 triblock copolymer, uniformly stirring, and continuously stirring for 24 hours at room temperature to obtain sol;
(3) adding 8g of citric acid monohydrate into the sol obtained in the step (2), and continuously stirring for 12 hours at room temperature to completely dissolve the citric acid monohydrate to obtain sol with metal ions uniformly complexed;
(4) placing the complex sol obtained in the step (3) in a drying oven, keeping the temperature at 110 ℃ for 2h, raising the temperature to 160 ℃ and keeping the temperature for 2h, and finally raising the temperature to 230 ℃ and keeping the temperature for 5h to obtain dry gel at the temperature rise rate of 2 ℃/min;
(5) and (4) placing the dried gel obtained in the step (4) in a muffle furnace, gradually increasing the roasting heat preservation temperature at the temperature rise rate of 2 ℃/min all the time, naturally cooling to room temperature between each heat preservation platform, and then heating to the next heat preservation platform. The roasting heat preservation platform is used for preserving heat at 170 ℃ for 11h, at 260 ℃ for 3h, at 370 ℃ for 1h, at 460 ℃ for 2h and at 700 ℃ for 2h in sequence to obtain the nano composite oxide.
Example 3
Preparing a nano composite oxide according to the method of the embodiment 1, except that the complex sol obtained in the step (3) is placed in a drying oven, and is kept at 100 ℃ for 1h, 180 ℃ and 1h at a temperature rise rate of 4 ℃/min all the time, and is finally kept at 240 ℃ for 6h, and the sol is dried and partially oxidized to obtain dry gel;
(5) and (4) placing the dried gel obtained in the step (4) in a muffle furnace, gradually increasing the roasting heat preservation temperature at a temperature rise rate of 4 ℃/min all the time, naturally cooling to room temperature between each heat preservation platform, and then heating to the next heat preservation platform. The roasting heat preservation platform is sequentially used for preserving heat at 180 ℃ for 10 hours, preserving heat at 280 ℃ for 2 hours, preserving heat at 380 ℃ for 1 hour, preserving heat at 480 ℃ for 1 hour and preserving heat at 900 ℃ for 1 hour to obtain the nano composite oxide.
Example 4
The preparation of the nanocomposite oxide was carried out in the same manner as in example 1, except that the drying was carried out in a one-step temperature raising manner, wherein the temperature raising rate was 3 ℃/min. After heating to 220 ℃, drying for 8 h.
Example 5
The preparation of the nanocomposite oxide was carried out as in example 1, except that the calcination was carried out in a one-step temperature rise manner, wherein the temperature rise rate was 3 ℃/min. After the temperature is raised to 900 ℃, roasting is carried out for 5 hours.
Example 6
Preparation of nanocomposite oxide was carried out in the same manner as in example 1, except that, during firing, there was no step of cooling to room temperature at each warming stage.
Example 7
Preparation of a nanocomposite oxide was carried out in the same manner as in example 1, except that the weight of n-butanol was 16g, the weight of P123 was 4g, and the weight of citric acid monohydrate was 8 g.
Example 8
A nanocomposite oxide was prepared by the method of example 1, except that the weight of n-butanol was 12g, the weight of P123 was 2.4g, and the weight of citric acid monohydrate was 8 g.
Example 9
Preparation of a nanocomposite oxide was carried out in the same manner as in example 1, except that the weight of n-butanol was 10g, the weight of P123 was 5g, and the weight of citric acid monohydrate was 4 g.
Comparative example 1
The preparation of the nanocomposite oxide was carried out according to the method of example 1, except that citric acid monohydrate was not added.
Comparative example 2
Fe was weighed according to the molar ratio of Fe, Co and Cr in example 12O3、CoO and Cr2O3The preparation of the nano composite oxide is carried out by adopting a solid phase and high-energy ball milling method, which comprises the following steps: mixing, grinding, tabletting, heating to 900 deg.C at a heating rate of 10 deg.C/min, calcining for 10 hr, high-energy ball milling with ethanol as medium, and drying to obtain nanometer composite oxide.
Test example 1
The nitrogen adsorption and desorption experiments of the nanocomposite oxide samples obtained in the examples and comparative examples were carried out on an ASAP2020 type fully automatic physical and chemical adsorption analyzer manufactured by Micromeritics, usa. The samples were activated for 10 hours at 300 ℃ before measurement. The specific surface area of the sample was calculated by the BET method, and the pore volume and the average pore diameter were calculated by the BJH model, and the results are shown in table 1.
Test example 2
The nanocomposite oxides obtained in the examples were subjected to X-ray powder diffractometry tests using a copper target with a characteristic spectral wavelength Cu K on a Bruker D8 Adti diffractometerα1.5418 angstroms
Figure BDA0002698975390000121
The XRD patterns of the nanocomposite oxides obtained in examples 1 to 5 have characteristic peaks at 2 θ of 18.4, 30.3 °, 35.7 °, 37.3 °, 43.4 °, 53.8 °, 57.4 °, 63 ° and 90.4 °, and the measurement error is ± 0.2 °. It can be seen from the XRD patterns of examples 1 to 8 that the nanocomposite oxide obtained in each example is spinel-type crystals, and the composite oxide obtained in example 9 is mostly a hetero phase and does not completely form a spinel-structured composite oxide, wherein the XRD pattern of the nanocomposite oxide obtained in example 1 has characteristic peaks at 2 θ of 18.4, 30.3 °, 35.7 °, 37.3 °, 43.4 °, 53.8 °, 57.4 °, 63 ° and 90.4 °, and the X-ray diffraction pattern of the nanocomposite oxide obtained in example 1 is shown in fig. 1.
Test example 3
The nanocomposite oxides in the examples were subjected to Transmission Electron Microscope (TEM) testing, and transmission electron micrographs were obtained on a JEOL JEM-2100 transmission electron microscope at an acceleration voltage of 200 kV. The particle diameter of the nanocomposite oxide was measured from the obtained transmission electron micrograph. The test results obtained are shown in Table 1.
The transmission electron microscope picture obtained in example 1 is shown in FIG. 2.
Test example 4
The nano composite oxides obtained in the examples and the comparative examples are used for treating organic matters in sewage, and the specific steps are as follows: in a fixed bed reactor, in the presence of ozone, the sewage is contacted with the obtained nano composite oxide to carry out catalytic reaction. Based on 1 ton of sewage, the using amount of the ozone is 2m3(ii) a The temperature of the catalytic reaction is 25 ℃; the contact time is 0.5 h; the concentration of the ozone is 30mg/L, and the flow rate is 0.1L/min.
The COD of the treated sewage is measured according to the method recommended by the dichromate determination of chemical oxygen demand of water (GB 11914-1989), and the obtained test results are shown in Table 1;
wherein the COD removal rate (COD of the pre-treatment wastewater-COD of the post-treatment wastewater)/COD of the pre-treatment wastewater is 100%
TABLE 1
Figure BDA0002698975390000131
As can be seen from Table 1, examples 1-9, using the technical solution of the present application, can obtain a nanocomposite oxide with a spinel crystal structure, however, as can be seen from comparison of examples 1 to 4 and 7 to 9 with examples 5 to 6, the nanocomposite oxides obtained by different firing methods have different particle size distributions and texture characteristics, for example, the average pore diameter of the nano composite oxide particles obtained by one-step roasting is far larger than that of the nano composite oxide particles obtained by multi-step roasting, and the specific surface area, the pore volume and the average pore diameter are far smaller than those of the nano composite oxide particles obtained by multi-step roasting, therefore, when the catalysts obtained in the respective examples were used for water treatment, the treatment effects of examples 1 to 4 and 7 to 9 were superior to those of examples 5 to 6, and the COD removal rate of the treated sewage was high. The nanocomposite oxide particles obtained in examples 1 to 9 were examined to have a small particle size and a uniform particle size.
In addition, it was confirmed that comparative example 1 did not form a nano composite oxide having a spinel-type crystal structure, and the COD removal rate of the treated sewage was small when it was used for sewage treatment. The COD removal rate of the treated sewage obtained by using the product obtained in the comparative example 2 in sewage treatment is also lower than that of the treated sewage obtained in the examples 1-9. It was examined that the nanocomposite oxide particles obtained in comparative examples 1 and 2 were large in particle size and non-uniform in particle size.
Comparing example 1 with other examples and comparative examples, it can be seen that the nanocomposite oxide with the best performance can be obtained according to the most preferred embodiment comprising the following steps:
(1) mixing Fe (NO)3)3·9H2O、Co(NO3)2·6H2O and Cr (NO)3)3·9H2Adding O into concentrated nitric acid with the weight fraction of 64-65 wt% and the temperature of 89-90 ℃, and stirring to completely dissolve the O;
(2) adding the mixed nitrate solution obtained in the step (1) into n-butanol, uniformly stirring, then adding the P123 triblock copolymer, uniformly stirring, and continuously stirring at room temperature for 23-24h to obtain sol;
(3) adding citric acid monohydrate into the sol obtained in the step (2), and continuously stirring for 11-12h at room temperature to completely dissolve the citric acid monohydrate to obtain sol with metal ions uniformly complexed;
(4) placing the complex sol obtained in the step (3) in a drying oven, keeping the temperature of 120-122 ℃ for 1.9-2h, raising the temperature to 148-150 ℃ and keeping the temperature for 1.8-2h, and finally raising the temperature to 220-221 ℃ and keeping the temperature for 4.9-5h to obtain dry gel at the temperature rise rate of 2-2.1 ℃/min;
(5) and (3) placing the dried gel obtained in the step (4) in a muffle furnace, gradually increasing the roasting heat preservation temperature at the temperature rise rate of 2-2.2 ℃/min all the time, naturally cooling to 25-25.3 ℃ between each heat preservation platform, and then raising the temperature to the next heat preservation platform. The roasting heat preservation platform is sequentially used for preserving heat for 11.9-12h at the temperature of 150-150.2 ℃, 2.8-3h at the temperature of 249-250 ℃, 2-2.1h at the temperature of 350-352 ℃, 1-1.1h at the temperature of 450-451 ℃ and 1.9-2h at the temperature of 800-801 ℃ to obtain the nano composite oxide;
wherein, with respect to 0.005mol Fe (NO)3)3·9H2O，Co(NO3)2·6H2The amount of O is 0.005-0.0051mol, Cr (NO)3)3·9H2The dosage of O is 0.005-0.0052mol, the dosage of concentrated nitric acid is 2-2.2g, the dosage of n-butanol is 13.9-14g, the dosage of P123 is 2.9-3g, and the dosage of citric acid monohydrate is 7.9-8 g.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (13)

1. A method for producing a nanocomposite oxide, characterized by comprising: mixing an iron precursor, a cobalt precursor, an optional chromium precursor, a dispersion medium, a template agent and a complexing agent for a complexing reaction, and then drying and roasting the mixture in sequence to obtain the nano composite oxide.
2. The method of claim 1, wherein the complexing further comprises adding a chromium precursor to perform the complexing;
preferably, the iron precursor, the cobalt precursor, and the optional chromium precursor are used in a molar ratio of 1: 1-2: 0-2, preferably 1: 1-1.25: 1-1.5;
preferably, the average particle diameter of the nanocomposite oxide is 10 to 5000nm, preferably 20 to 100 nm.
3. The method according to claim 1 or 2, wherein the amounts of the dispersion medium, the templating agent and the complexing agent are such that the weight ratio of the dispersion medium, the templating agent and the complexing agent is from 1.5 to 2: 0.3-0.5: 1;
and/or the iron precursor and the template are used in amounts such that the weight ratio of the iron precursor to the template is 0.5-1: 1.
4. the method according to any one of claims 1-3, wherein the method further comprises: dissolving the iron precursor, the cobalt precursor, and the optional chromium precursor under acidic conditions;
preferably, the acidic conditions are controlled using an acidic substance, which is nitric acid and/or hydrochloric acid;
preferably, the acidic substance is used in an amount of 0.00125 to 0.03mol in terms of hydrogen ion, based on 0.005mol of the cobalt precursor;
preferably, the acidic substance is provided in the form of a solution having a weight fraction of 65-68 wt.%;
preferably, the temperature of the dissolution is 70-90 ℃.
5. The method according to any one of claims 1 to 4, wherein the iron precursor is a water-soluble iron salt, preferably at least one selected from the group consisting of ferric nitrate, ferric chloride and ferric acetate;
and/or the cobalt precursor is a water-soluble cobalt salt, preferably at least one selected from cobalt nitrate, cobalt chloride and cobalt acetate;
and/or the chromium precursor is a water-soluble chromium salt, preferably at least one selected from chromium nitrate, chromium chloride and chromium acetate;
and/or, the template agent is a nonionic surfactant; preferably having the formula EOaPObEOaThe polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer of (a); more preferably, wherein a has a value of 10 to 100, b has a value of 40 to 80; EO is particularly preferred20PO70EO20；
And/or the dispersion medium is n-butanol and/or n-pentanol;
and/or the complexing agent is citric acid.
6. The method according to any one of claims 1 to 5, wherein the time of the complexation reaction is 24 to 48 hours;
preferably, the iron precursor, the cobalt precursor, the optional chromium precursor, the dispersion medium and the template are firstly contacted to obtain a first sol, and then the first sol is secondly contacted with the complexing agent to obtain a second sol;
preferably, the time of the first contact is 12-24h, and the time of the second contact is 12-24 h.
7. The method according to any one of claims 1 to 6, wherein the heating rate of the drying is 2 to 4 ℃/min, and the temperature of the drying is 100 to 220 ℃;
preferably, the drying mode is as follows: heating to 100-120 ℃ at a heating rate of 2-4 ℃/min, preserving heat for 1-2h, heating to 150-180 ℃, preserving heat for 1-2h, heating to 220-240 ℃, and preserving heat for 5-6 h;
and/or the heating rate of the roasting is 2-4 ℃/min, and the roasting temperature is 150-900 ℃;
preferably, the roasting mode is as follows: heating to 150-180 ℃ at a heating rate of 2-4 ℃/min, preserving heat for 10-12h, heating to 250-280 ℃, preserving heat for 2-3h, heating to 350-380 ℃, preserving heat for 1-2h, heating to 450-480 ℃, preserving heat for 1-2h, finally heating to 700-900 ℃, and preserving heat for 1-2 h;
preferably, the temperature is cooled to 20-40 ℃ between each heat-preservation platform, and then the temperature is raised to the next heat-preservation platform.
8. A nanocomposite oxide, characterized in that it is obtained by a process according to any one of claims 1 to 7.
9. A method of wastewater treatment, the method comprising: contacting the sewage with the nano composite oxide of claim 8 in the presence of ozone to perform a catalytic reaction;
alternatively, a nanocomposite oxide is produced according to the method of any one of claims 1 to 7, and then the wastewater is brought into contact with the obtained nanocomposite oxide in the presence of ozone to perform a catalytic reaction.
10. The method according to claim 9, wherein the amount of ozone is 1.5-2.5m based on 1 ton of wastewater3；
And/or the temperature of the catalytic reaction is 20-40 ℃; the contact time is 0.5-1 h; the concentration of the ozone is 30-40mg/L, and the flow rate is 0.1-0.5L/min.
11. A nanocomposite oxide obtained by the method according to any one of claims 1 to 7 and use of the nanocomposite oxide according to claim 8 in water treatment.
12. A nanocomposite oxide comprising Fe, Co and optionally Cr, wherein the nanocomposite oxide has an XRD pattern with characteristic peaks at 18.4 ± 0.2 °, 30.3 ± 0.2 °, 35.7 ± 0.2 °, 37.3 ± 0.2 °, 43.4 ± 0.2 °, 53.8 ± 0.2 °, 57.4 ± 0.2 °, 63 ± 0.2 ° and 90.4 ± 0.2 ° 2 Θ.
13. The nanocomposite oxide according to claim 12, wherein the nanocomposite oxide has a specific surface area of 1 to 20m2A/g, preferably of from 15 to 18m2/g；
And/or the pore volume of the nano composite oxide is 0.0005-0.2cm3In g, preferably from 0.15 to 0.18cm3/g；
And/or the average pore diameter of the nano composite oxide is 5-400nm, preferably 230-380 nm;
and/or the average particle diameter of the nano composite oxide is 10-5000nm, preferably 20-100 nm;
preferably, the nanocomposite oxide is spinel-type crystals, and the molar ratio of Fe, Co and Cr in the nanocomposite oxide is 1: 1-2: 0-2, preferably 1: 1-1.25: 1-1.5.
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