CN107552066B - Fe-Mn-Zr composite oxide catalyst and preparation method and application thereof - Google Patents
Fe-Mn-Zr composite oxide catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a Fe-Mn-Zr composite oxide catalyst and a preparation method and application thereof, and adopts a simple coprecipitation method to calcine at 500 ℃ by taking isopropanolamine as a precipitator, thereby successfully preparing the Fe-Mn-Zr composite oxide catalyst which is MnFe doped with Zr2O4A spinel-type composite oxide catalyst. The catalyst can achieve higher NO and CO conversion rate at lower temperature, the preparation method is simple and easy to implement, and the preparation raw materials are cheap and easy to obtain. In particular, according to the molar ratio of Fe, Mn and Zr 2: 2: 1, the conversion rate of NO at 300 ℃ is 100%, and the conversion rate of CO at 400 ℃ is 100%, so that the catalyst shows ideal catalytic activity of CO + NO, and is beneficial to the development of non-noble metal catalysts in the aspect of exhaust emission control.
Description
Technical Field
The invention relates to the field of non-noble metal catalysts, in particular to a Fe-Mn-Zr composite oxide catalyst and a preparation method and application thereof.
Background
The problem of air pollution has received much attention in recent years. The exhaust gas of automobiles contains NOxAnd toxic components such as CO and the like, which are harmful to human health and harm the atmosphere and ecological environment, so that the treatment of automobile exhaust pollution becomes one of the most urgent tasks in current environmental management. The CO + NO catalytic reaction (CO catalytic reduction of NO) is an effective method for simultaneously removing NO and CO in automobile exhaust, and the selection of the catalyst used in the reaction is a crucial factor for influencing the treatment effect of the automobile exhaust.
Noble metal catalysts (e.g., Pd, Rh, Pt, etc.) have long been considered to be the most effective catalysts for the CO + NO catalytic reaction. However, as market demand increases, noble metal catalysts are difficult to be widely used in practical production processes, mainly due to their scarcity, high cost, low thermal stability, and non-regenerability after deactivation. In order to overcome the above problems, there has been increasing interest in developing new non-noble metal catalysts to replace noble metal catalysts.
Non-noble metal catalysts can provide adsorption sites or catalytically active sites (e.g., oxygen vacancies), and their excellent redox properties have been widely discussed and used in the catalytic arts. AB containing 3d transition metal ions in various non-noble metal oxides2O4Spinel-type metal oxides of formula (I) have unique surface and structural properties and are useful in removing NOxHas high catalytic activity. Research and development of AB prepared in the prior art2O4The spinel type metal oxide has catalytic activity and stability of about 60% of NO and CO conversion rate at low temperature (350 ℃), so that the preparation of the spinel type metal oxide catalyst with high NO and CO conversion rate at lower temperature still has important significance.
Disclosure of Invention
The invention provides a spinel composite oxide Fe/Mn/Zr catalyst, and a preparation method and application thereof, and aims to solve the problem that a non-noble metal catalyst has low NO and CO conversion rate at low temperature in a CO + NO catalytic reaction.
In a first aspect, the present invention provides a Fe-Mn-Zr composite oxide catalyst, which is MnFe doped with Zr2O4A spinel-type composite oxide catalyst.
In a second aspect, the present invention also provides a method for producing the Fe-Mn-Zr composite oxide catalyst according to the first aspect, comprising the steps of:
(1) according to the molar ratio of Fe, Mn and Zr, 1: (0.25-1): (0.25-1), weighing ferric salt, manganese salt and zirconium salt; dissolving the ferric salt into ferric salt solution formed by deionized water, dissolving the manganese salt into manganese salt solution formed by mixed solution of deionized water and hydrochloric acid, and dissolving the zirconium salt into zirconium salt solution formed by mixed solution of deionized water and hydrochloric acid; uniformly mixing the ferric salt solution, the manganese salt solution and the zirconium salt solution under magnetic stirring at 50 ℃ to form a metal salt solution;
(2) according to the molar ratio of Fe to isopropanolamine of 1: (30-60), weighing isopropanolamine, preparing an isopropanolamine solution by using deionized water, and keeping the temperature of the isopropanolamine solution at 90 ℃ for standby;
(3) rapidly adding the metal salt solution into the isopropanolamine solution under the condition of vigorous magnetic stirring at 90 ℃ to obtain a suspension, continuously stirring for 2 hours, and performing vacuum filtration to obtain a filter cake;
(4) and washing the filter cake with deionized water and absolute ethyl alcohol, drying in a forced air drying oven at 60 ℃ for 12 hours, and calcining in an argon atmosphere at 500 ℃ for 3 hours to obtain the Fe-Mn-Zr composite oxide catalyst.
Optionally, the iron salt is ferric chloride; the manganese salt is manganese chloride; the zirconium salt is zirconium nitrate.
Optionally, the concentration of the ferric salt solution is 0.25-0.5 mol/L, the concentration of the manganese salt solution is 1-4 mol/L, the concentration of the zirconium salt solution is 1-4 mol/L, and the concentration of the isopropanolamine solution is 3 mol/L.
Optionally, the mixed volume of the iron salt solution is 40mL, the mixed volumes of the manganese salt solution and the zirconium salt solution are both 5mL, and the mixed volume of the isopropanolamine solution is 200 mL.
Optionally, in the mixed solution of deionized water and hydrochloric acid, the hydrochloric acid is 37% by mass, and the volume ratio of hydrochloric acid to deionized water is 1: 4.
preferably, the method is performed as follows: according to the mol ratio of Fe, Mn, Zr and isopropanolamine 2: 2: 1: 60, weighing 20mmol FeCl3·6H2Dissolving O in 40mL of deionized water to form FeCl3Weighing 20mmol MnCl2Dissolving in a mixed solution of 1mLHCl and 4mL deionized water to form MnCl2Weighing 10mmol of Zr (NO)3)4Dissolved in a mixed solution of 1mL HCl and 4mL deionized water to form Zr (NO)3)4Solution of FeCl3Solution, MnCl2Solution and Zr (NO)3)4The solution is evenly mixed under the magnetic stirring at 50 ℃ to form a metal salt solution; 200mL of isopropanolamine with the concentration of 3mol/L is prepared, and the isopropanolamine solution is placed at 90 ℃ for heat preservation for standby; rapidly adding a metal salt solution into an isopropanolamine solution under the condition of vigorous magnetic stirring at 90 ℃ to obtain a suspension, continuously stirring for 2 hours, and carrying out vacuum filtration to obtain a filter cake; washing the filter cake with deionized water and absolute ethyl alcohol, drying in a forced air drying oven at 60 ℃ for 12 hours, and calcining in an argon atmosphere at 500 ℃ for 3 hours to obtain the Fe-Mn-Zr composite oxide catalyst.
In a third aspect, the invention also provides an application of the Fe-Mn-Zr composite oxide catalyst in the first aspect, which is characterized in that the Fe-Mn-Zr composite oxide catalyst is applied to CO and NO in automobile exhaustxAnd (4) removing.
Preferably, the molar ratio of Fe, Mn and Zr is 2: 2: 1, the conversion rate of NO at 300 ℃ is 100 percent, and the conversion rate of CO at 400 ℃ is 100 percent.
The invention has the following beneficial effects:
the invention adopts a simple coprecipitation method to calcine at 500 ℃ by taking isopropanolamine (MIPA) as a precipitator, and successfully prepares the Fe-Mn-Zr composite oxide catalyst, wherein the catalyst is MnFe doped with Zr2O4A spinel-type composite oxide catalyst. The catalyst can achieve higher NO and CO conversion rate at lower temperature, the preparation method is simple and easy to implement, and the preparation raw materials are cheap and easy to obtain. In particular, according to the molar ratio of Fe, Mn and Zr 2: 2: 1, the conversion rate of NO at 300 ℃ is 100%, and the conversion rate of CO at 400 ℃ is 100%, so that the catalyst shows ideal catalytic activity of CO + NO, and is beneficial to the development of non-noble metal catalysts in the aspect of exhaust emission control.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious to those skilled in the art that other drawings can be obtained according to the drawings without any inventive exercise.
FIG. 1 is an XRD pattern of the product provided in examples and comparative examples of the present invention, wherein the reference numerals indicate: (a) FMZ-0, (b) FMZ-1, (c) FMZ-2, (d) FMZ-3, (e) FMZ-4, (f) FMZ-5, (g) FMZ-6;
FIG. 2 is a TEM image of the products provided in examples and comparative examples of the present invention, wherein the reference numerals indicate: (a) FMZ-0, (b) FMZ-1, (c) FMZ-2, (d) FMZ-3, (e) FMZ-4, (f) FMZ-5, (g) FMZ-6;
FIG. 3 shows XPS survey spectra of the products of example 5 and comparative example of the present invention.
FIG. 4 is a CO + NO catalysis plot of the product provided in example 5 of the present invention.
Detailed Description
The invention provides a spinel composite oxide Fe/Mn/Zr catalyst, and a preparation method and application thereof, which are used for solving the problem that a non-noble metal catalyst has low NO and CO conversion rate at low temperature in a CO + NO catalytic reaction. The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of the Fe-Mn-Zr composite oxide catalyst comprises the following steps:
(1) according to the mol ratio of Fe, Mn and Zr 2: 1: 1, weighing 20mmol FeCl3·6H2Dissolving O in 40mL of deionized water to form FeCl3Weighing 10mmol MnCl2Dissolved in a mixed solution of 1mL of HCl (mass fraction of 37%) and 4mL of deionized water to form MnCl2Weighing 10mmol of Zr (NO)3)4Dissolve in 1mL HCl and 4mL deionizationIn the mixed solution of the water, Zr (NO) is formed3)4Solution of FeCl3Solution, MnCl2Solution and Zr (NO)3)4The solution was mixed well under magnetic stirring at 50 ℃ to form a metal salt solution.
(2) According to the molar ratio of Fe to isopropanolamine of 2: and 60, preparing 200mL of 3mol/L isopropanolamine, and keeping the temperature of the isopropanolamine solution at 90 ℃ for later use.
(3) And under the condition of vigorous magnetic stirring at 90 ℃, quickly adding a metal salt solution into an isopropanolamine solution to obtain a turbid liquid, continuously stirring for 2 hours, and carrying out vacuum filtration to obtain a filter cake.
(4) Washing the filter cake with deionized water and absolute ethyl alcohol, drying in a forced air drying oven at 60 ℃ for 12 hours, and calcining in an argon atmosphere at 500 ℃ for 3 hours to obtain the Fe-Mn-Zr composite oxide catalyst FMZ-1.
Method for evaluating catalytic activity:
the CO + NO oxidation reduction catalysis performance test instrument of Fe-Mn-Zr comprises: continuous phase fixed bed microreactor, gas chromatograph, thermocouple, quartz tube reactor (length 40cm, inner diameter 6 mm). At atmospheric pressure, 50mg of catalyst particles and 300mg of quartz sand were weighed and mixed uniformly, and placed in a quartz tube reactor. The composition of the reaction gas was NO (1000ppm) -CO (1200ppm) with Ar as the equilibrium gas. The flow rate of the gas was controlled to be 60000mL/(h gcat), and the temperature programming rate was 1.7 ℃/min. The temperature of the reactor was monitored in real time by a thermocouple, and the content of the product of the catalytic reaction was monitored on-line by a gas chromatograph.
The catalytic activity of FMZ-1 prepared in example 1 was evaluated in the manner described above, and the following conclusions were made: the maximum conversion of FMZ-1 to CO at 350 ℃ was 100% and to NO at 425 ℃xThe highest conversion of (a) was 40%.
Example 2
A preparation method of the Fe-Mn-Zr composite oxide catalyst comprises the following steps:
(1) according to the molar ratio of Fe, Mn and Zr of 1: 1: 1, weighing 10mmol FeCl3·6H2Dissolving O in 40mL of deionized water to form FeCl3Solution, weighing 10mmol MnCl2Dissolved in a mixed solution of 1mL of HCl (mass fraction of 37%) and 4mL of deionized water to form MnCl2Weighing 10mmol of Zr (NO)3)4Dissolved in a mixed solution of 1mL HCl and 4mL deionized water to form Zr (NO)3)4Solution of FeCl3Solution, MnCl2Solution and Zr (NO)3)4The solution was mixed well under magnetic stirring at 50 ℃ to form a metal salt solution.
(2) According to the molar ratio of Fe to isopropanolamine of 1: and 60, preparing 200mL of 3mol/L isopropanolamine, and keeping the temperature of the isopropanolamine solution at 90 ℃ for later use.
(3) And under the condition of vigorous magnetic stirring at 90 ℃, quickly adding a metal salt solution into an isopropanolamine solution to obtain a turbid liquid, continuously stirring for 2 hours, and carrying out vacuum filtration to obtain a filter cake.
(4) Washing the filter cake with deionized water and absolute ethyl alcohol, drying in a forced air drying oven at 60 ℃ for 12 hours, and calcining in an argon atmosphere at 500 ℃ for 3 hours to obtain the Fe-Mn-Zr composite oxide catalyst, which is named as FMZ-2.
The catalytic activity of FMZ-2 prepared in example 2 was evaluated as described above, with the following conclusions: FMZ-2 for CO and NO at 400 deg.CxThe highest conversion was 90% and 30%, respectively.
Example 3
A preparation method of the Fe-Mn-Zr composite oxide catalyst comprises the following steps:
(1) according to the mol ratio of Fe, Mn and Zr 2: 1: 2, weighing 20mmol FeCl3·6H2Dissolving O in 40mL of deionized water to form FeCl3Weighing 10mmol MnCl2Dissolved in a mixed solution of 1mL of HCl (mass fraction of 37%) and 4mL of deionized water to form MnCl2Weighing 20mmol of Zr (NO)3)4Dissolved in a mixed solution of 1mL HCl and 4mL deionized water to form Zr (NO)3)4Solution of FeCl3Solution, MnCl2Solution and Zr (NO)3)4The solution was mixed well under magnetic stirring at 50 ℃ to form a metal salt solution.
(2) According to the molar ratio of Fe to isopropanolamine of 2: and 60, preparing 200mL of 3mol/L isopropanolamine, and keeping the temperature of the isopropanolamine solution at 90 ℃ for later use.
(3) And under the condition of vigorous magnetic stirring at 90 ℃, quickly adding a metal salt solution into an isopropanolamine solution to obtain a turbid liquid, continuously stirring for 2 hours, and carrying out vacuum filtration to obtain a filter cake.
(4) Washing the filter cake with deionized water and absolute ethyl alcohol, drying in a forced air drying oven at 60 ℃ for 12 hours, and calcining in an argon atmosphere at 500 ℃ for 3 hours to obtain the Fe-Mn-Zr composite oxide catalyst, which is named as FMZ-3.
The catalytic activity of FMZ-3 prepared in example 3 was evaluated as described above, with the following conclusions: the highest conversion of FMZ-3 to CO at 400 ℃ was 75% and to NO at 340 ℃xThe highest conversion of (a) is 90%.
Example 4
A preparation method of the Fe-Mn-Zr composite oxide catalyst comprises the following steps:
(1) according to the mol ratio of Fe, Mn and Zr 2: 0.5: 1, weighing 20mmol FeCl3·6H2Dissolving O in 40mL of deionized water to form FeCl3Weighing 5mmol of MnCl2Dissolved in a mixed solution of 1mL of HCl (mass fraction of 37%) and 4mL of deionized water to form MnCl2Weighing 10mmol of Zr (NO)3)4Dissolved in a mixed solution of 1mL HCl and 4mL deionized water to form Zr (NO)3)4Solution of FeCl3Solution, MnCl2Solution and Zr (NO)3)4The solution was mixed well under magnetic stirring at 50 ℃ to form a metal salt solution.
(2) According to the molar ratio of Fe to isopropanolamine of 2: and 60, preparing 200mL of 3mol/L isopropanolamine, and keeping the temperature of the isopropanolamine solution at 90 ℃ for later use.
(3) And under the condition of vigorous magnetic stirring at 90 ℃, quickly adding a metal salt solution into an isopropanolamine solution to obtain a turbid liquid, continuously stirring for 2 hours, and carrying out vacuum filtration to obtain a filter cake.
(4) Washing the filter cake with deionized water and absolute ethyl alcohol, drying in a forced air drying oven at 60 ℃ for 12 hours, and calcining in an argon atmosphere at 500 ℃ for 3 hours to obtain the Fe-Mn-Zr composite oxide catalyst, which is named as FMZ-4.
FMZ-4 prepared in example 4 was evaluated for catalytic activity as described above, with the following conclusions: the maximum conversion of FMZ-4 to CO at 350 ℃ is 100%, and to NO at 450 ℃xThe highest conversion of (a) is 60%.
Example 5
A preparation method of the Fe-Mn-Zr composite oxide catalyst comprises the following steps:
(1) according to the mol ratio of Fe, Mn and Zr 2: 2: 1, weighing 20mmol FeCl3·6H2Dissolving O in 40mL of deionized water to form FeCl3Weighing 20mmol MnCl2Dissolved in a mixed solution of 1mL of HCl (mass fraction of 37%) and 4mL of deionized water to form MnCl2Weighing 10mmol of Zr (NO)3)4Dissolved in a mixed solution of 1mL HCl and 4mL deionized water to form Zr (NO)3)4Solution of FeCl3Solution, MnCl2Solution and Zr (NO)3)4The solution was mixed well under magnetic stirring at 50 ℃ to form a metal salt solution.
(2) According to the molar ratio of Fe to isopropanolamine of 2: and 60, preparing 200mL of 3mol/L isopropanolamine, and keeping the temperature of the isopropanolamine solution at 90 ℃ for later use.
(3) And under the condition of vigorous magnetic stirring at 90 ℃, quickly adding a metal salt solution into an isopropanolamine solution to obtain a turbid liquid, continuously stirring for 2 hours, and carrying out vacuum filtration to obtain a filter cake.
(4) Washing the filter cake with deionized water and absolute ethyl alcohol, drying in a forced air drying oven at 60 ℃ for 12 hours, and calcining in an argon atmosphere at 500 ℃ for 3 hours to obtain the Fe-Mn-Zr composite oxide catalyst, which is named as FMZ-5.
FMZ-5, prepared in example 5, was evaluated for catalytic activity in the manner described above, with the following conclusions: the maximum conversion of FMZ-5 to CO at 400 ℃ is 100%, and to NO at 300 ℃xThe highest conversion of (a) is 100%.The catalyst prepared by the method has good catalytic performance. In particular, see fig. 4, the CO + NO catalysis pattern for the product provided in example 5.
Example 6
A preparation method of the Fe-Mn-Zr composite oxide catalyst comprises the following steps:
(1) according to the mol ratio of Fe, Mn and Zr 2: 1: 0.5 weighing 20mmol FeCl3·6H2Dissolving O in 40mL of deionized water to form FeCl3Weighing 10mmol MnCl2Dissolved in a mixed solution of 1mL of HCl (mass fraction of 37%) and 4mL of deionized water to form MnCl2Weighing 5mmol of Zr (NO)3)4Dissolved in a mixed solution of 1mL HCl and 4mL deionized water to form Zr (NO)3)4Solution of FeCl3Solution, MnCl2Solution and Zr (NO)3)4The solution was mixed well under magnetic stirring at 50 ℃ to form a metal salt solution.
(2) According to the molar ratio of Fe to isopropanolamine of 2: and 60, preparing 200mL of 3mol/L isopropanolamine, and keeping the temperature of the isopropanolamine solution at 90 ℃ for later use.
(3) And under the condition of vigorous magnetic stirring at 90 ℃, quickly adding a metal salt solution into an isopropanolamine solution to obtain a turbid liquid, continuously stirring for 2 hours, and carrying out vacuum filtration to obtain a filter cake.
(4) Washing the filter cake with deionized water and absolute ethyl alcohol, drying in a forced air drying oven at 60 ℃ for 12 hours, and calcining in an argon atmosphere at 500 ℃ for 3 hours to obtain the Fe-Mn-Zr composite oxide catalyst, which is named as FMZ-6.
FMZ-5, prepared in example 6, was evaluated for catalytic activity in the manner described above, with the following conclusions: the maximum conversion of FMZ-6 to CO at 400 ℃ is 90% and to NO at 325 ℃xThe highest conversion of (a) is 100%.
Comparative example
A preparation method of the Fe-Mn composite oxide catalyst comprises the following steps:
(1) according to the molar ratio of Fe to Mn of 2: 1, weighing 20mmol FeCl3·6H2O dissolved in 40In mL of deionized water, FeCl is formed3Weighing 10mmol MnCl2Dissolved in a mixed solution of 1mL of HCl (mass fraction of 37%) and 4mL of deionized water to form MnCl2Solution of FeCl3Solution and MnCl2The solution was mixed well under magnetic stirring at 50 ℃ to form a metal salt solution.
(2) According to the molar ratio of Fe to isopropanolamine of 2: and 60, preparing 200mL of 3mol/L isopropanolamine, and keeping the temperature of the isopropanolamine solution at 90 ℃ for later use.
(3) And under the condition of vigorous magnetic stirring at 90 ℃, quickly adding a metal salt solution into an isopropanolamine solution to obtain a turbid liquid, continuously stirring for 2 hours, and carrying out vacuum filtration to obtain a filter cake.
(4) Washing the filter cake with deionized water and absolute ethyl alcohol, drying in a forced air drying oven at 60 ℃ for 12 hours, and calcining in an argon atmosphere at 500 ℃ for 3 hours to obtain the Fe-Mn-Zr composite oxide catalyst FMZ-0.
The catalytic activity of FMZ-0 prepared in the comparative example was evaluated in the manner described above, and the results were as follows: FMZ-0 for CO and NO at 400 deg.CxThe highest conversion was 60.1% and 20.4%, respectively.
In addition, XRD (X-ray diffraction), TEM (transmission electron microscope), and XPS (X-ray photoelectron spectroscopy) spectrum tests were performed on the catalysts obtained in the above examples and comparative examples, and the results were as follows:
pure MnFe2O4(a) And the XRD pattern of the Zr-doped (b-g) Fe-Mn-Zr composite oxide catalyst product is shown in FIG. 1. The main peaks of all products are attributed to the (220), (311), (400), (511) and (440) crystal planes at 30.62 °, 36.05 °, 43.72 °, 57.72 °, 63.32 °, respectively. The characteristic peak of 7 groups of XRD corresponds to MnFe2O4Standard peak of (JPCDSNo. 10-0319). No other impure phases were observed in the range of detection by XRD instrument, indicating that the transition metal entered MnFe2O4A crystal lattice.
The morphology of the products prepared with different metal ratios is shown in figure 2. The product we prepared by precipitation is an aggregate of fine particles with no apparent morphological differences. Thus, the difference in metal ratios has very little effect on the morphology of the product. The formation of aggregates may be due to the removal of nano-stabilizing ions from the product by water washing, alcohol washing or calcination processes.
The XPS plots of the products of example 5 and comparative example are shown in FIG. 3, and we can see that the elements Fe, Mn, Zr, O and Fe, Mn, O are present in FMZ-5 and FMZ-0, respectively. Illustrating the doping of the zirconium element into the product prepared by the present invention. The products from the other examples were subjected to XPS testing, the results of which are similar to those of FIG. 3 and are not shown again.
Finally, Table 1 lists the reduction performance of the prepared Fe-Mn-Zr composite oxide catalyst compared with that of the different catalysts. The temperature window of the prepared Fe-Mn-Zr composite oxide catalyst is wider compared with other catalysts for CO reduction of NO.
TABLE 1 comparison of the reducing Properties of different catalysts
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the disclosure herein. This invention is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
It will be understood that the invention is not limited to the precise arrangements described above and shown in the drawings and that various modifications and changes may be made without departing from the scope thereof. The scope of the invention is limited only by the appended claims.
Claims (8)
1. Fe-Mn-Zr composite oxide catalystThe preparation method of the agent is characterized in that the catalyst is MnFe doped by Zr2O4The preparation method of the spinel-type composite oxide catalyst comprises the following steps:
(1) according to the molar ratio of Fe, Mn and Zr, 1: (0.25-1): (0.25-1), weighing ferric salt, manganese salt and zirconium salt; dissolving the ferric salt into ferric salt solution formed by deionized water, dissolving the manganese salt into manganese salt solution formed by mixed solution of deionized water and hydrochloric acid, and dissolving the zirconium salt into zirconium salt solution formed by mixed solution of deionized water and hydrochloric acid; uniformly mixing the ferric salt solution, the manganese salt solution and the zirconium salt solution under magnetic stirring at 50 ℃ to form a metal salt solution;
(2) according to the molar ratio of Fe to isopropanolamine of 1: (30-60), weighing isopropanolamine, preparing an isopropanolamine solution by using deionized water, and keeping the temperature of the isopropanolamine solution at 90 ℃ for standby;
(3) rapidly adding the metal salt solution into the isopropanolamine solution under the condition of vigorous magnetic stirring at 90 ℃ to obtain a suspension, continuously stirring for 2 hours, and performing vacuum filtration to obtain a filter cake;
(4) and washing the filter cake with deionized water and absolute ethyl alcohol, drying in a forced air drying oven at 60 ℃ for 12 hours, and calcining in an argon atmosphere at 500 ℃ for 3 hours to obtain the Fe-Mn-Zr composite oxide catalyst.
2. The method of producing an Fe-Mn-Zr composite oxide catalyst according to claim 1, characterized in that said iron salt is ferric chloride; the manganese salt is manganese chloride; the zirconium salt is zirconium nitrate.
3. The method of preparing an Fe-Mn-Zr composite oxide catalyst according to claim 1, wherein the concentration of the iron salt solution is 0.25 to 0.5mol/L, the concentration of the manganese salt solution is 1 to 4mol/L, the concentration of the zirconium salt solution is 1 to 4mol/L, and the concentration of the isopropanolamine solution is 3 mol/L.
4. The method of preparing an Fe-Mn-Zr composite oxide catalyst according to claim 3, wherein the mixed volume of said iron salt solution is 40mL, the mixed volumes of said manganese salt solution and zirconium salt solution are both 5mL, and the mixed volume of said isopropanolamine solution is 200 mL.
5. The method of preparing an Fe-Mn-Zr composite oxide catalyst according to claim 1, wherein in the mixed solution of deionized water and hydrochloric acid, the hydrochloric acid is 37% by mass, and the volume ratio of hydrochloric acid to deionized water is 1: 4.
6. the method of producing an Fe-Mn-Zr composite oxide catalyst according to claim 1, characterized in that it is carried out as follows:
according to the mol ratio of Fe, Mn, Zr and isopropanolamine 2: 2: 1: 60, weighing 20mmol FeCl3·6H2Dissolving O in 40mL of deionized water to form FeCl3Weighing 20mmol MnCl2Dissolved in a mixed solution of 1mL HCl and 4mL deionized water to form MnCl2Weighing 10mmol of Zr (NO)3)4Dissolved in a mixed solution of 1mL HCl and 4mL deionized water to form Zr (NO)3)4Solution of FeCl3Solution, MnCl2Solution and Zr (NO)3)4The solution is evenly mixed under the magnetic stirring at 50 ℃ to form a metal salt solution; 200mL of isopropanolamine with the concentration of 3mol/L is prepared, and the isopropanolamine solution is placed at 90 ℃ for heat preservation for standby; rapidly adding a metal salt solution into an isopropanolamine solution under the condition of vigorous magnetic stirring at 90 ℃ to obtain a suspension, continuously stirring for 2 hours, and carrying out vacuum filtration to obtain a filter cake; washing the filter cake with deionized water and absolute ethyl alcohol, drying in a forced air drying oven at 60 ℃ for 12 hours, and calcining in an argon atmosphere at 500 ℃ for 3 hours to obtain the Fe-Mn-Zr composite oxide catalyst.
7. Use of the Fe-Mn-Zr composite oxide catalyst according to claim 1, characterized in that it is used for CO and NO in automobile exhaustxAnd (4) removing.
8. Use of the Fe-Mn-Zr composite oxide catalyst according to claim 7, characterized in that the molar ratio of Fe, Mn and Zr is 2: 2: 1, the conversion rate of NO at 300 ℃ is 100 percent, and the conversion rate of CO at 400 ℃ is 100 percent.
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