CN112573569B - Rare earth composite oxide with high heat resistance and preparation method thereof - Google Patents

Rare earth composite oxide with high heat resistance and preparation method thereof Download PDF

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CN112573569B
CN112573569B CN202011539157.3A CN202011539157A CN112573569B CN 112573569 B CN112573569 B CN 112573569B CN 202011539157 A CN202011539157 A CN 202011539157A CN 112573569 B CN112573569 B CN 112573569B
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rare earth
sulfate
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zirconium
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谭志伟
黄英强
陈涛
谭程校
梁景棠
万国江
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Jiangmen Kanhoo Industry Co ltd
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Abstract

The invention provides a rare earth composite oxide with high heat resistance and a preparation method thereof, belonging to the field of rare earth materials. The rare earth composite oxide comprises the following components in parts by weight: 50-90 parts of ZrO25 to 40 parts of CeO25-20 parts of rare earth oxide except cerium oxide and 0-10 parts of transition metal oxide. According to the invention, sulfate is added in two steps at the early stage, and the structure regulator is added at the later stage to control the granularity, the pore size distribution, the specific surface area and the pore volume of the rare earth composite oxide, and simultaneously increase the thermal stability of the rare earth composite oxide.

Description

Rare earth composite oxide with high heat resistance and preparation method thereof
Technical Field
The invention relates to a rare earth composite oxide with high heat resistance and a preparation method thereof, belonging to the field of rare earth materials.
Background
The rare earth composite oxide is a multifunctional material with unique structure and performance, and is widely applied to the industrial fields of ceramic materials, catalytic materials, electrolyte materials and the like. The catalytic material and the electrolyte material of the fuel cell need to work under high temperature condition, and have high requirement on the heat resistance of the rare earth composite oxide. In the field of volatile organic compound treatment, the rare earth composite oxide is usually used as a carrier and an oxygen storage material of noble metal, and flameless combustion is carried out on hydrocarbon at 250-500 ℃ for a long time. The rare earth composite oxide needs to have a hierarchical pore structure and a large specific surface area to improve the dispersion load capacity of the noble metal and provide an oxygen transmission channel; in the application of automobile exhaust purification, the rare earth composite oxide is the most common oxygen storage material in the current automobile catalyst, and a higher surface area must be maintained even under the severe aging condition of more than 1000 ℃. Otherwise, the rare earth composite oxide can cause the violent reduction of oxygen storage performance and the embedding of noble metal due to sintering; yttria-zirconia is the most classical electrolyte material in the field of solid oxide fuel cells. The zirconium yttrium composite oxide can reduce the operating temperature of the fuel cell by the thinning of the electrolyte, but it is necessary to operate under a high temperature condition of 800 ℃. Aging of the electrolyte material at high temperatures causes a sharp drop in the conductivity of the electrolyte. The rare earth composite oxide with high thermal stability has wide application in various fields, and has very important significance in developing the green and environment-friendly preparation technology of the material.
The industrial preparation method of the rare earth composite oxide mainly comprises an ammonia-water complex coprecipitation method, a sulfate radical complex coprecipitation method and a hydrothermal method at present. The ammonia water complex coprecipitation method is characterized in that ammonia water is used as a precipitator, a mixed solution of zirconium and rare earth ions is dripped into the ammonia water for precipitation reaction, hydroxide precipitate with uniformly distributed elements is obtained, and then the hydroxide precursor is roasted at high temperature to obtain a composite oxide with large specific surface area; the hydrothermal method is to crystallize the amorphous hydroxide powder after the coprecipitation reaction is finished under the conditions of high temperature and high pressure to obtain the hydroxide powder with high crystallinity. Then, carrying out high-temperature roasting to obtain a finished product of the composite oxide; the sulfate coordination coprecipitation method is to coordinate sulfate and zirconium ions into a complex, then to use sodium hydroxide as a precipitator to carry out precipitation conversion on zirconium and rare earth elements to obtain a porous hydroxide precursor, and then to carry out roasting to obtain the product.
Different production methods of rare earth composite oxides have limitations and disadvantages, such as environmental protection, high cost, poor heat resistance, and the like. The ammonia water complex coprecipitation method is a production method mainly adopted by domestic manufacturers at present, and has the advantages of simple production equipment, high efficiency, good product performance and the like. The patent (CN 102791632B) reports the use of ammonia as a precipitantPreparing the zirconium-cerium composite oxide by a reverse coprecipitation method, wherein the specific surface area of the rare earth composite oxide can reach 55-60 m after the rare earth composite oxide is calcined for 4 hours at 1000 DEG C2(ii) in terms of/g. However, ammonia water is used as a precipitator in the method, and ammonia gas escapes in the production process to cause air pollution and generate a large amount of high-concentration ammonia nitrogen wastewater. Under the situation that the national security and environmental supervision is stricter at present, the production method needs to add expensive environmental protection equipment to treat waste gas and waste water, so that the production cost is increased. The hydrothermal method is a common method for preparing the composite oxide, and the prepared powder has the advantages of high crystallinity and uniform particle size distribution. The patent (CN 110026178B) reports that the rare earth composite oxide synthesized by using a hydrothermal method has a specific surface area of about 60m after being aged at 950 ℃ for 6 hours2(ii) in terms of/g. The hydrothermal method has a disadvantage in that the powder needs to be treated under high temperature and high pressure for a long time. The requirement on production equipment is high, the utilization efficiency of the reaction kettle is low, and the production cost is high. Patent (CN 105339307B) reports the preparation of zirconia-based porous bodies using a sulfate coordination co-precipitation method. The preparation method has the advantages of large pore volume and weak agglomeration of the product. But the specific surface area of the material is relatively low and the thermal stability is poor.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the rare earth composite oxide with adjustable pore distribution and high heat resistance and the preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: a rare earth composite oxide comprises the following components in parts by weight: 50-90 parts of ZrO25 to 40 parts of CeO25-20 parts of rare earth oxide except cerium oxide and 0-10 parts of transition metal oxide.
The relative content of cerium and zirconium in the rare earth composite oxide determines not only the crystal phase thereof, but also the specific surface area, the redox performance and the thermal stability of the rare earth composite oxide. The third component is introduced into the rare earth composite oxide system, so that lattice defects can be further increased, the oxygen storage capacity of the rare earth composite oxide is improved, the transformation of the crystal phase of the rare earth composite oxide can be inhibited, and the thermal stability of the rare earth composite oxide is improved.
As a preferable embodiment of the rare earth composite oxide of the present invention, the rare earth oxide other than ceria is at least one of yttria, lanthana, praseodymia, and neodymia; the transition metal in the transition metal oxide is at least one of niobium, manganese, iron, cobalt, nickel and copper.
Because cerium is a rare earth element, the cerium-zirconium solid solution is doped with other rare earth elements to easily form a multi-element solid solution, and the fluorite structure of the cerium-zirconium material can be reserved; meanwhile, the generation of lattice defects can be increased, and the specific surface area and the thermal stability of the rare earth composite oxide are increased. The transition metal has an unfilled valence layer orbit, the property is obviously different from other elements, the transition metal can be used as a modified element of the rare earth composite oxide, the transition metal is introduced into the rare earth composite oxide to form a solid solution structure, and the modified rare earth composite oxide has better low-temperature redox performance.
In addition, the invention also provides a preparation method of the rare earth composite oxide, which comprises the following steps:
adding sulfate into a zirconium salt solution at room temperature, heating to 80-100 ℃, and then preserving heat for 10-60 min to obtain basic zirconium sulfate sol;
(2) adding a sulfate solution into the basic zirconium sulfate sol obtained in the step (1), and then curing for 15-120 min to form a basic zirconium sulfate precursor;
(3) cooling the basic zirconium sulfate precursor obtained in the step (2) to below 70 ℃, then adding a rare earth salt solution and a transition metal salt solution, and uniformly stirring to obtain a mixed metal salt solution;
(4) adding an alkali solution into the mixed metal salt solution obtained in the step (3), and adjusting the pH value to be more than or equal to 12 to obtain a rare earth composite hydroxide precipitate;
(5) washing the rare earth composite hydroxide precipitate obtained in the step (4) to remove impurities, dispersing the precipitate in a solvent again, adding a structure regulator at 25-70 ℃, and continuously stirring for 30-60 min to obtain rare earth composite hydroxide slurry;
(6) and (4) filtering and drying the rare earth composite hydroxide slurry obtained in the step (5), roasting at 700 ℃ for 4h, and crushing to obtain the rare earth composite oxide.
In the prior art of a sulfate coordination coprecipitation method, a preparation method of basic zirconium sulfate is to directly add a sulfate solution into a zirconium salt solution in one step, and the pore size of the basic zirconium sulfate cannot be adjusted, so that the specific surface area of the prepared rare earth composite oxide is relatively low. The inventor of the application finds that a small amount of sulfate radical is added into a zirconium salt solution, and zirconium ions can form basic zirconium sulfate sol after the temperature is raised to be higher than 80 ℃ and is kept for a period of time. The basic zirconium sulfate is present in the solution in the form of fine crystal nuclei. Then, the solution of the sulfate salt is continuously added into the basic zirconium sulfate sol. At this time, the sulfate radical connects basic zirconium sulfate crystal nuclei to each other, so that a basic zirconium sulfate precursor with a macroporous structure is formed. The rare earth composite oxide prepared by the basic zirconium sulfate precursor with the macroporous structure in the subsequent process also has the macroporous structure. However, the macropores of the rare earth composite oxide material are easy to collapse after aging at a high temperature of more than 1000 ℃, so that the specific surface area after aging is sharply reduced. The inventor of the application discovers that self-assembly rearrangement can occur between crystal grains when the structure regulator is used for complexing the surface of the composite hydroxide crystal grains, the stacking structure of the crystal grains becomes compact, and macropores shrink to become micropores. Therefore, the rare earth composite hydroxide stabilizes the bulk structure while maintaining a large specific surface area, which can be maintained at all even after aging at high temperatures of 1000 ℃ or higher. In addition, the pore size distribution of the material can be controlled by adjusting the addition amount of the sulfate in the step (1) and the addition amount of the structure regulator in the step (5), so that the pore size distribution can be adapted to different application requirements.
As a preferable embodiment of the rare earth composite oxide of the present invention, the zirconium salt in the zirconium salt solution of the step (1) is zirconium oxychloride or zirconium nitrate.
As a preferred embodiment of the rare earth composite oxide of the present invention, in the step (1), the sulfate is at least one of zirconium sulfate, sodium sulfate, and potassium sulfate; sulfate radical accounts for 8-23% of the weight of the zirconium dioxide.
The addition amount of sulfate radicals can influence the structure of the rare earth composite oxide, the addition amount of sulfate radicals is too small, the formed basic zirconium sulfate microcrystal is too small, and the influence on the structure of the basic zirconium sulfate precursor formed in the step (2) that the structure does not have a macroporous structure is avoided; when the amount of the sulfate radical added is too large, zirconium ions are precipitated out of the solution in a large amount.
As a preferred embodiment of the rare earth composite oxide of the present invention, the sulfate in the sulfate solution in step (2) is at least one of sodium sulfate and potassium sulfate; sulfate radical accounts for 12-46% of the weight of the zirconium dioxide; the mass fraction of sulfate in the sulfate solution is 5-20 wt%.
Free zirconium ions also exist in the basic zirconium sulfate sol obtained in the step (1), and the zirconium ions can be converted into a basic zirconium sulfate precursor by further adding sulfate, and basic zirconium sulfate crystal nuclei in the basic zirconium sulfate sol are connected to form the basic zirconium sulfate precursor with a macroporous structure.
As a preferred embodiment of the rare earth composite oxide of the present invention, the rare earth salt and the transition metal salt in the rare earth salt solution and the transition metal salt solution of step (3) are chloride salts or nitrate salts; the mass fraction of the rare earth salt and the transition metal salt in the rare earth salt solution and the transition metal salt solution is 10-30 wt%.
As a preferred embodiment of the rare earth composite oxide of the present invention, in the alkali solution in the step (4), the alkali is at least one of sodium hydroxide, potassium hydroxide and lithium hydroxide; the mass fraction of alkali in the alkali solution is 10-30 wt%.
In a preferred embodiment of the rare earth composite oxide according to the present invention, the solvent in the step (5) is at least one of water and ethanol.
As a preferred embodiment of the rare earth composite oxide of the present invention, the structure-regulating agent in the step (5) is at least one of a β -diketone compound, a fatty amine, and a fatty acid; the beta-diketone compound is at least one of stearoylbenzoylmethane, ethyl acetylacetonate, 4, 6-dioxoheptanoic acid, di-tert-valerylmethane, 2, 4-octanedione and dibenzoylmethane; the fatty acid is at least one of caprylic acid, pelargonic acid, capric acid, lauric acid, stearic acid, oleic acid and citric acid; the fatty amine is at least one of lauryl amine, oleyl amine, trioctyl decyl tertiary amine, n-decyl amine, tetramethyl ammonium hydroxide and hexadecyl trimethyl ammonium hydroxide; the structural regulator accounts for 20-50% of the weight of the porous rare earth composite oxide.
The beta-diketone compound has two oxygen atoms with strong coordination function, is a good metal chelating agent, can form stable chelate with rare earth metal, and simultaneously has good auxiliary heat stabilization function. Beta diketone, fatty acid and fatty amine can perform coordination reaction with metal on the surface of the rare earth composite hydroxide particles, so that the beta diketone, the fatty acid and the fatty amine are grafted on the surface of the particles, and the particles are changed from hydrophilicity to lipophilicity. Therefore, the particles after surface modification are packed together, and the structure becomes compact.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, the rare earth composite oxide with adjustable pore size and pore size distribution, large specific surface area and high thermal stability is prepared by adding sulfate step by step at the early stage, adding a structure regulator at the later stage and controlling the addition amounts of the sulfate and the structure regulator.
Drawings
FIG. 1 is a pore size distribution diagram of rare earth composite oxides prepared in example 1 and comparative examples 1 to 4;
FIG. 2 is an SEM photograph of a rare earth composite oxide prepared in example 1;
fig. 3 is an SEM image of the rare earth composite oxide prepared in comparative example 3.
Detailed Description
Example 1
The rare earth composite oxide comprises the following components in parts by weight: 60 parts of zirconium dioxide, 30 parts of cerium dioxide, 2 parts of lanthanum oxide and 8 parts of yttrium oxide.
The preparation method of the rare earth composite oxide in the embodiment comprises the following steps:
(1) adding potassium sulfate into a zirconium nitrate solution with the mass fraction of 2 wt%, wherein the sulfate radical accounts for 23% of the weight of the zirconium dioxide; stirring until potassium sulfate solid is completely dissolved, heating the solution to 100 ℃, and then preserving heat for 60min to obtain basic zirconium sulfate sol;
(2) adding 5 wt% potassium sulfate solution into the basic zirconium sulfate sol obtained in the step (1), wherein sulfate radical accounts for 12% of the weight of zirconium dioxide; curing for 60min at 100 ℃ to obtain a basic zirconium sulfate precursor;
(3) cooling the basic zirconium sulfate precursor obtained in the step (2) to 50 ℃, adding a cerium nitrate solution, a lanthanum nitrate solution and a yttrium nitrate solution, and uniformly stirring and mixing to obtain a mixed metal salt solution;
(4) adding a sodium hydroxide solution with the mass fraction of 25 wt% into the mixed metal salt solution obtained in the step (3), and adjusting the pH to 12 to obtain a rare earth composite hydroxide precipitate;
(5) washing the rare earth composite hydroxide precipitate obtained in the step (4) to remove impurities; then re-dispersing the mixture in absolute ethyl alcohol by using a high-speed dispersing agent; then heating to 50 ℃, adding stearoylbenzoylmethane and dodecylamine, and continuing stirring for 60min to obtain rare earth composite hydroxide slurry; the total adding amount of the stearoylbenzoylmethane and the dodecylamine is 50 percent of the weight of the rare earth composite oxide, and the weight ratio of the stearoylbenzoylmethane to the dodecylamine is 2: 1;
(6) and (4) filtering and drying the rare earth composite hydroxide slurry obtained in the step (5), roasting at 700 ℃ for 4h, and crushing to obtain the rare earth composite oxide.
Example 2
The rare earth composite oxide comprises the following components in parts by weight: 60 parts of zirconium dioxide, 30 parts of cerium dioxide, 2 parts of lanthanum oxide and 8 parts of yttrium oxide.
The preparation method of the rare earth composite oxide in the embodiment comprises the following steps:
(1) adding potassium sulfate into a zirconium nitrate solution with the mass fraction of 2 wt%, wherein the sulfate radical accounts for 8% of the weight of the zirconium dioxide; stirring until potassium sulfate solid is completely dissolved, heating the solution to 100 ℃, and then preserving heat for 120min to obtain basic zirconium sulfate sol;
(2) adding 5 wt% potassium sulfate solution into the basic zirconium sulfate sol obtained in the step (1), wherein sulfate is 46% of the weight of zirconium dioxide; curing for 60min at 100 ℃ to obtain a basic zirconium sulfate precursor;
(3) cooling the basic zirconium sulfate precursor obtained in the step (2) to 50 ℃, adding a cerium nitrate solution, a lanthanum nitrate solution and a yttrium nitrate solution, and uniformly stirring and mixing to obtain a mixed metal salt solution;
(4) and (4) adding a 25 wt% sodium hydroxide solution into the mixed metal salt solution obtained in the step (3), and adjusting the pH to 13.5 to obtain a rare earth composite hydroxide precipitate.
(5) Washing the rare earth composite hydroxide precipitate obtained in the step (4) to remove impurities; then re-dispersing the mixture in absolute ethyl alcohol by using a high-speed dispersing agent; then heating the slurry to 50 ℃, adding stearoylbenzoylmethane and dodecylamine, and continuing stirring for 60min to obtain rare earth composite hydroxide slurry; the total adding amount of the stearoylbenzoylmethane and the dodecylamine is 20 percent of the weight of the rare earth composite oxide, and the weight ratio of the stearoylbenzoylmethane to the dodecylamine is 2: 1;
(6) and (4) filtering and drying the rare earth composite hydroxide slurry obtained in the step (5), roasting at 700 ℃ for 4h, and crushing to obtain the rare earth composite oxide.
Example 3
The rare earth composite oxide comprises the following components in parts by weight: 90 parts of zirconium dioxide, 5 parts of cerium dioxide and 5 parts of yttrium oxide.
The preparation method of the rare earth composite oxide in the embodiment comprises the following steps:
(1) adding zirconium sulfate into a zirconium oxychloride solution with the mass fraction of 5 wt%, wherein the sulfate radical accounts for 16% of the weight of the zirconium dioxide; stirring until the zirconium sulfate solid is completely dissolved, heating the solution to 95 ℃, and then preserving heat for 60min to obtain basic zirconium sulfate sol;
(2) adding a sodium sulfate solution with the mass fraction of 20 wt% into the basic zirconium sulfate sol obtained in the step (1), wherein sulfate radicals are 24% of the weight of zirconium dioxide; curing for 60min at 100 ℃ to obtain a basic zirconium sulfate precursor;
(3) cooling the basic zirconium sulfate precursor obtained in the step (2) to 50 ℃, adding a cerium chloride solution and a yttrium chloride solution, and uniformly stirring and mixing to obtain a mixed metal salt solution;
(4) adding a sodium hydroxide solution with the mass fraction of 10 wt% into the mixed metal salt solution obtained in the step (3), and adjusting the pH to 14 to obtain a rare earth composite hydroxide precipitate;
(5) washing the rare earth composite hydroxide precipitate obtained in the step (4) to remove impurities; then re-dispersing the mixture in absolute ethyl alcohol by using a high-speed dispersing agent; then heating the slurry to 50 ℃, adding dodecanoic acid and tetramethylammonium hydroxide, and continuing stirring for 60min to obtain rare earth composite hydroxide slurry; the total adding amount of the dodecanoic acid and the tetramethylammonium hydroxide is 40 percent of the weight of the rare earth composite oxide, and the weight ratio of the dodecanoic acid to the tetramethylammonium hydroxide is 2.2: 1;
(6) and (4) filtering and drying the rare earth composite hydroxide slurry obtained in the step (5), roasting at 700 ℃ for 4h, and crushing to obtain the rare earth composite oxide.
Example 4
The rare earth composite oxide comprises the following components in parts by weight: 60 parts of zirconium dioxide, 25 parts of cerium dioxide, 4 parts of lanthanum oxide, 6 parts of yttrium oxide and 5 parts of manganese dioxide.
The preparation method of the rare earth composite oxide in the embodiment comprises the following steps:
(1) adding sodium sulfate into a zirconium oxychloride solution with the mass fraction of 5 wt%, wherein the sulfate radical accounts for 22% of the weight of the zirconium dioxide; stirring until the sodium sulfate solid is completely dissolved, heating the solution to 90 ℃, and then preserving heat for 15min to obtain basic zirconium sulfate sol;
(2) adding a sodium sulfate solution with the mass fraction of 15 wt% into the basic zirconium sulfate sol obtained in the step (1), wherein sulfate radicals are 22% of the weight of zirconium dioxide; curing for 60min at 100 ℃ to obtain a basic zirconium sulfate precursor;
(3) cooling the basic zirconium sulfate precursor obtained in the step (2) to 40 ℃, adding cerium chloride, lanthanum chloride, yttrium chloride and manganese chloride solution, and stirring and mixing uniformly to obtain mixed metal salt solution;
(4) adding a sodium hydroxide solution with the mass fraction of 30wt% into the mixed metal salt solution obtained in the step (3), and adjusting the pH to 13 to obtain a rare earth composite hydroxide precipitate;
(5) washing the rare earth composite hydroxide precipitate obtained in the step (4) to remove impurities; then re-dispersing the mixture in water by using a high-speed dispersing agent; adding dodecylamine and citric acid at room temperature, and continuously stirring for 60min to obtain rare earth composite hydroxide slurry; the total adding amount of the laurylamine and the citric acid is 50 percent of the weight of the rare earth composite oxide, and the weight ratio of the laurylamine to the citric acid is 2.89: 1;
(6) and (4) filtering and drying the rare earth composite hydroxide slurry obtained in the step (5), roasting at 700 ℃ for 4h, and crushing to obtain the rare earth composite oxide.
Example 5
The rare earth composite oxide comprises the following components in parts by weight: 50 parts of zirconium dioxide, 25 parts of cerium dioxide, 5 parts of lanthanum oxide, 10 parts of yttrium oxide and 10 parts of copper oxide.
The preparation method of the rare earth composite oxide in the embodiment comprises the following steps:
(1) adding sodium sulfate into a zirconium oxychloride solution with the mass fraction of 4 wt%, wherein the sulfate radical accounts for 22% of the weight of the zirconium dioxide; stirring until the zirconium sulfate solid is completely dissolved, heating the solution to 90 ℃, and then preserving heat for 15min to obtain basic zirconium sulfate sol;
(2) adding a sodium sulfate solution with the mass fraction of 15 wt% into the basic zirconium sulfate sol obtained in the step (1), wherein sulfate radicals are 22% of the weight of zirconium dioxide; curing for 60min at 100 ℃ to obtain a basic zirconium sulfate precursor;
(3) cooling the basic zirconium sulfate precursor obtained in the step (2) to 40 ℃, adding cerium chloride, lanthanum chloride, praseodymium chloride, yttrium chloride and copper chloride solution, and uniformly stirring and mixing to obtain mixed metal salt solution;
(4) adding a sodium hydroxide solution with the mass fraction of 20 wt% into the mixed metal salt solution obtained in the step (3), and adjusting the pH value to 12.5 to obtain a rare earth composite hydroxide precipitate;
(5) washing the rare earth composite hydroxide precipitate obtained in the step (4) to remove impurities; then re-dispersing the mixture in ethanol by using a high-speed dispersing agent; then heating the slurry to 60 ℃, adding dodecanoic acid and dodecylamine, and continuing stirring for 30min to obtain rare earth composite hydroxide slurry; the total adding amount of the dodecanoic acid and the dodecylamine is 35 percent of the weight of the rare earth composite oxide, and the weight ratio of the dodecanoic acid to the dodecylamine is 1.08: 1;
(6) and (4) filtering and drying the rare earth composite hydroxide slurry obtained in the step (5), roasting at 700 ℃ for 4h, and crushing to obtain the rare earth composite oxide.
Example 6
The rare earth composite oxide comprises the following components in parts by weight: 50 parts of zirconium dioxide, 40 parts of cerium dioxide, 5 parts of lanthanum oxide and 5 parts of yttrium oxide.
The preparation method of the rare earth composite oxide in the embodiment comprises the following steps:
(1) adding sodium sulfate into a zirconium oxychloride solution with the mass fraction of 5 wt%, wherein the sulfate radical accounts for 22% of the weight of the zirconium dioxide; stirring until the zirconium sulfate solid is completely dissolved, heating the solution to 80 ℃, and then preserving heat for 60min to obtain basic zirconium sulfate sol;
(2) adding a sodium sulfate solution with the mass fraction of 15 wt% into the basic zirconium sulfate sol obtained in the step (1), wherein sulfate radicals are 22% of the weight of zirconium dioxide; curing for 120min at 100 ℃ to obtain a basic zirconium sulfate precursor;
(3) cooling the basic zirconium sulfate precursor obtained in the step (2) to 60 ℃, adding a cerium chloride solution, a lanthanum chloride solution and a yttrium chloride solution, and uniformly stirring and mixing to obtain a mixed metal salt solution;
(4) adding a sodium hydroxide solution with the mass fraction of 20 wt% into the mixed metal salt solution obtained in the step (3), and adjusting the pH value to 12 to obtain a rare earth composite hydroxide precipitate;
(5) washing the rare earth composite hydroxide precipitate obtained in the step (4) to remove impurities; then re-dispersing the mixture in water by using a high-speed dispersing agent; then heating the slurry to 70 ℃, adding dodecanoic acid and tetramethylammonium hydroxide, and continuing stirring for 30min to obtain rare earth composite hydroxide slurry; the total adding amount of the dodecanoic acid and the tetramethylammonium hydroxide is 30 percent of the weight of the rare earth composite oxide, and the weight ratio of the dodecanoic acid to the tetramethylammonium hydroxide is 2.19: 1;
(6) and (4) filtering and drying the rare earth composite hydroxide slurry obtained in the step (5), roasting at 700 ℃ for 4h, and crushing to obtain the rare earth composite oxide.
Example 7
The rare earth composite oxide comprises the following components in parts by weight: 60 parts of zirconium dioxide, 20 parts of cerium dioxide, 8 parts of lanthanum oxide and 12 parts of yttrium oxide.
The preparation method of the rare earth composite oxide in the embodiment comprises the following steps:
(1) adding sodium sulfate into a zirconium oxychloride solution with the mass fraction of 5 wt%, wherein the sulfate radical accounts for 22% of the weight of the zirconium dioxide; stirring until the zirconium sulfate solid is completely dissolved, heating the solution to 100 ℃, and then preserving heat for 10min to obtain basic zirconium sulfate sol;
(2) adding a sodium sulfate solution with the mass fraction of 15 wt% into the basic zirconium sulfate sol obtained in the step (1), wherein sulfate radicals are 22% of the weight of zirconium dioxide; curing for 15min at 100 ℃ to obtain a basic zirconium sulfate precursor;
(3) cooling the basic zirconium sulfate precursor obtained in the step (2) to 60 ℃, adding a cerium chloride solution, a lanthanum chloride solution and a yttrium chloride solution, and uniformly stirring and mixing to obtain a mixed metal salt solution;
(4) adding a sodium hydroxide solution with the mass fraction of 20 wt% into the mixed metal salt solution obtained in the step (3), and adjusting the pH value to 13.5 to obtain rare earth composite hydroxide precipitate;
(5) washing the rare earth composite hydroxide precipitate obtained in the step (4) to remove impurities; then re-dispersing the mixture in water by using a high-speed dispersing agent; then heating the slurry to 60 ℃, adding dodecanoic acid and tetramethylammonium hydroxide, and continuing stirring for 30min to obtain rare earth composite hydroxide slurry; the total adding amount of the dodecanoic acid and the tetramethylammonium hydroxide is 30 percent of the weight of the rare earth composite oxide, and the weight ratio of the dodecanoic acid to the tetramethylammonium hydroxide is 2.19: 1;
(6) and (4) filtering and drying the rare earth composite hydroxide slurry obtained in the step (5), roasting at 700 ℃ for 4h, and crushing to obtain the rare earth composite oxide.
Example 8
The rare earth composite oxide comprises the following components in parts by weight: 70 parts of zirconium dioxide, 20 parts of cerium dioxide, 5 parts of lanthanum oxide and 10 parts of yttrium oxide.
The preparation method of the rare earth composite oxide in the embodiment comprises the following steps:
(1) adding sodium sulfate into a zirconium oxychloride solution with the mass fraction of 4.5 wt%, wherein the sulfate radical accounts for 22% of the weight of the zirconium dioxide; stirring until the zirconium sulfate solid is completely dissolved, heating the solution to 100 ℃, and then preserving heat for 10min to obtain basic zirconium sulfate sol;
(2) adding a sodium sulfate solution with the mass fraction of 15 wt% into the basic zirconium sulfate sol obtained in the step (1), wherein the sulfate radical accounts for 25% of the weight of the zirconium dioxide; curing for 15min at 100 ℃ to obtain a basic zirconium sulfate precursor;
(3) cooling the basic zirconium sulfate precursor obtained in the step (2) to 7 ℃, adding a cerium chloride solution, a lanthanum chloride solution and a yttrium chloride solution, and uniformly stirring and mixing to obtain a mixed metal salt solution;
(4) and (4) adding a sodium hydroxide solution with the mass fraction of 20 wt% into the mixed metal salt solution obtained in the step (3), and adjusting the pH value to 12 to obtain the rare earth composite hydroxide precipitate.
(5) Washing the rare earth composite hydroxide precipitate obtained in the step (4) to remove impurities; then re-dispersing the mixture in water by using a high-speed dispersing agent; then heating the slurry to 60 ℃, adding dodecanoic acid and tetramethylammonium hydroxide, and continuing stirring for 30min to obtain rare earth composite hydroxide slurry; the total adding amount of the stearoylbenzoylmethane and the tetramethylammonium hydroxide is 30 percent of the weight of the rare earth composite oxide, and the weight ratio of the stearoylbenzoylmethane to the tetramethylammonium hydroxide is 4.2: 1;
(6) and (4) filtering and drying the rare earth composite hydroxide slurry obtained in the step (5), roasting at 700 ℃ for 4h, and crushing to obtain the rare earth composite oxide.
Comparative example 1
The rare earth composite oxide of the comparative example comprises the following components in parts by weight: 60 parts of zirconium dioxide, 30 parts of cerium dioxide, 2 parts of lanthanum oxide and 8 parts of yttrium oxide.
The preparation method of the rare earth composite oxide of the comparative example comprises the following steps:
(1) adding potassium sulfate into a zirconium nitrate solution with the mass fraction of 2 wt%, wherein the sulfate radical accounts for 23% of the weight of the zirconium dioxide; stirring until potassium sulfate solid is completely dissolved, heating the solution to 100 ℃, and then preserving heat for 60min to obtain basic zirconium sulfate sol;
(2) adding 5 wt% potassium sulfate solution into the basic zirconium sulfate sol obtained in the step (1), wherein sulfate radical accounts for 12% of the weight of zirconium dioxide; curing for 60min at 100 ℃ to obtain a basic zirconium sulfate precursor;
(3) cooling the basic zirconium sulfate precursor obtained in the step (2) to 50 ℃, adding a cerium nitrate solution, a lanthanum nitrate solution and a yttrium nitrate solution, and uniformly stirring and mixing to obtain a mixed metal salt solution;
(4) adding a sodium hydroxide solution with the mass fraction of 25 wt% into the mixed metal salt solution obtained in the step (3), and adjusting the pH to 12 to obtain a rare earth composite hydroxide precipitate;
(5) and (4) washing the rare earth composite hydroxide precipitate obtained in the step (4) to remove impurities, roasting at 700 ℃ for 4h, and crushing to obtain the rare earth composite oxide.
Comparative example 2
The rare earth composite oxide of the comparative example comprises the following components in parts by weight: 60 parts of zirconium dioxide, 30 parts of cerium dioxide, 2 parts of lanthanum oxide and 8 parts of yttrium oxide.
The preparation method of the rare earth composite oxide of the comparative example comprises the following steps:
(1) heating a zirconium nitrate solution with the mass fraction of 2 wt% to 100 ℃, and then adding a potassium sulfate solution with the mass fraction of 5 wt% into the zirconium nitrate solution, wherein sulfate radicals are 35% of the weight of zirconium dioxide; curing for 60min at 100 ℃ to obtain a basic zirconium sulfate precursor;
(2) cooling the basic zirconium sulfate precursor obtained in the step (1) to 50 ℃, adding cerium nitrate, lanthanum nitrate and yttrium nitrate solution, and stirring and mixing uniformly to obtain mixed metal salt solution;
(3) adding a sodium hydroxide solution with the mass fraction of 25 wt% into the mixed metal salt solution obtained in the step (2), and adjusting the pH value to 12 to obtain a rare earth composite hydroxide precipitate;
(4) washing the rare earth composite hydroxide precipitate obtained in the step (3) to remove impurities; then re-dispersing the mixture in absolute ethyl alcohol by using a high-speed dispersing agent; then heating the slurry to 50 ℃, adding stearoylbenzoylmethane and dodecylamine, and continuing stirring for 60min to obtain rare earth composite hydroxide slurry; the total adding amount of the stearoylbenzoylmethane and the dodecylamine is 50 percent of the weight of the rare earth composite oxide, and the weight ratio of the stearoylbenzoylmethane to the dodecylamine is 2: 1;
(5) and (4) filtering and drying the rare earth composite hydroxide slurry obtained in the step (4), roasting at 700 ℃ for 4h, and crushing to obtain the rare earth composite oxide.
Comparative example 3
The rare earth composite oxide of the comparative example comprises the following components in parts by weight: 60 parts of zirconium dioxide, 25 parts of cerium dioxide, 2 parts of lanthanum oxide and 8 parts of yttrium oxide.
The preparation method of the rare earth composite oxide of the comparative example comprises the following steps:
(1) heating a zirconium nitrate solution with the mass fraction of 2 wt% to 100 ℃, and then adding a potassium sulfate solution with the mass fraction of 5 wt% into the zirconium nitrate solution, wherein sulfate radicals are 35% of the weight of zirconium dioxide; curing for 60min at 100 ℃ to obtain a basic zirconium sulfate precursor;
(2) and (2) cooling the basic zirconium sulfate precursor obtained in the step (1) to 50 ℃, adding cerium nitrate, lanthanum nitrate and yttrium nitrate solution, and stirring and mixing uniformly.
(3) Adding a sodium hydroxide solution with the mass fraction of 25 wt% into the mixed metal salt solution obtained in the step (2), and adjusting the pH value to 12 to obtain a rare earth composite hydroxide precipitate;
(4) washing the rare earth composite hydroxide precipitate obtained in the step (3) to remove impurities; roasting at 700 deg.c for 4 hr and crushing to obtain composite RE oxide.
Comparative example 4
The rare earth composite oxide of the comparative example comprises the following components in parts by weight: 60 parts of zirconium dioxide, 25 parts of cerium dioxide, 2 parts of lanthanum oxide and 8 parts of yttrium oxide.
The preparation method of the rare earth composite oxide of the comparative example comprises the following steps:
(1) adding potassium sulfate into a zirconium chloride solution with the mass fraction of 2 wt%, wherein the sulfate radical accounts for 4% of the weight of the zirconium dioxide; stirring until potassium sulfate solid is completely dissolved, heating the solution to 100 ℃, and then preserving heat for 60min to obtain basic zirconium sulfate sol;
(2) adding 5 wt% potassium sulfate solution into the basic zirconium sulfate sol obtained in the step (1), wherein the sulfate radical accounts for 31% of the weight of the zirconium dioxide; curing for 60min at 100 ℃ to obtain a basic zirconium sulfate precursor;
(3) cooling the basic zirconium sulfate precursor in the step (2) to 50 ℃, adding a cerium nitrate solution, a lanthanum nitrate solution and a yttrium nitrate solution, and uniformly stirring and mixing to obtain a mixed metal salt solution;
(4) adding a sodium hydroxide solution with the mass fraction of 25 wt% into the mixed metal salt solution obtained in the step (3), and adjusting the pH to 12 to obtain a rare earth composite hydroxide precipitate;
(5) washing the rare earth composite hydroxide precipitate obtained in the step (4) to remove impurities; then re-dispersing the mixture in absolute ethyl alcohol by using a high-speed dispersing agent; then heating the slurry to 50 ℃, adding stearoylbenzoylmethane and dodecylamine, and continuing stirring for 60min to obtain rare earth composite hydroxide slurry; the total adding amount of the stearoylbenzoylmethane and the dodecylamine is 50 percent of the weight of the rare earth composite oxide, and the weight ratio of the stearoylbenzoylmethane to the dodecylamine is 2: 1;
(6) and (4) filtering and drying the rare earth composite hydroxide slurry obtained in the step (5), roasting at 700 ℃ for 4h, and crushing to obtain the rare earth composite oxide.
Specific surface area and pore size distribution of the rare earth composite oxides of examples 1 to 8 and comparative examples 1 to 4 were measured at 77K using nitrogen as an adsorption gas using a TriStar 3020 full-automatic specific surface area and pore size analyzer, and the test results are shown in table 1. Wherein, before the nitrogen adsorption and desorption test, the rare earth composite oxide needs to be degassed at 200 ℃ for 2 hours to remove the water and air in the material pore channel, and then the detection is carried out; the specific surface area is calculated by a multipoint BET method, and the pore size distribution is calculated by a BJH method.
TABLE 1
Figure BDA0002854074800000151
Figure BDA0002854074800000161
As shown in Table 1, the rare earth composite oxide of the present invention has a particle size of 10 to 20 μm, a pore diameter of 24 to 28nm, and a specific surface area of 85 to 100m2A pore volume of 0.5 to 0.65 cm/g3(ii)/g; the specific surface area is 55-70 m after aging for 4 hours at 1000 DEG C2(ii)/g; the specific surface area is 30-40 m after aging for 4h at 1100 DEG C2/g。
Comparing the above example 1 with the comparative example 1, the example 1 with the comparative example 2, and the example 1 with the comparative example 3, respectively, it can be seen that the specific surface area, the pore volume, the pore diameter, and the specific surface area after high temperature aging of the product are remarkably improved by adding the structure-controlling agent to the rare earth composite oxide and adding the sulfate in two steps in the preparation method of the rare earth composite oxide.
FIG. 1 is a pore size distribution diagram of rare earth composite oxides prepared in example 1 and comparative examples 1 to 4; it can be seen from the figure that, in comparison with example 1, comparative example 1 was not modified with the structure-controlling agent, the amount of pores having a pore diameter of about 20nm was larger than that of example 1, and the amount of pores having a pore diameter of about 2nm was smaller than that of example 1. Illustrating that the structure modifiers can change macropores to micropores; the rare earth composite hydroxides of comparative examples 2 and 3 do not form a macroporous structure, and the amounts of pores having pore diameters of about 2nm and 20nm are smaller than those of example 1; in the step (1) of comparative example 4, only 4% of sodium sulfate was added, and pores having a pore diameter of about 20nm were formed less than in example 1.
Fig. 2 is an SEM image of the rare earth composite oxide prepared in example 1, and fig. 3 is an SEM image of the rare earth composite oxide prepared in comparative example 3; as is apparent from comparison between fig. 2 and 3, the rare earth composite oxide prepared in example 1 has a more uniform particle size and a spheroidal particle shape.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (8)

1. The preparation method of the rare earth composite oxide is characterized by comprising the following components in parts by weight: 50-90 parts of ZrO25 to 40 parts of CeO25-20 parts of rare earth oxide except cerium oxide and 0-10 parts of transition metal oxide;
the preparation method of the rare earth composite oxide comprises the following steps:
(1) adding sulfate into the zirconium salt solution at room temperature, wherein sulfate radicals are 8-23% of the weight of zirconium dioxide, heating to 80-100 ℃, and then preserving heat for 10-60 min to obtain basic zirconium sulfate sol;
(2) adding a sulfate solution into the basic zirconium sulfate sol obtained in the step (1), and then curing for 15-120 min to form a basic zirconium sulfate precursor;
(3) cooling the basic zirconium sulfate precursor obtained in the step (2) to below 70 ℃, then adding a rare earth salt solution and a transition metal salt solution, and uniformly stirring to obtain a mixed metal salt solution;
(4) adding an alkali solution into the mixed metal salt solution obtained in the step (3), and adjusting the pH value to be more than or equal to 12 to obtain a rare earth composite hydroxide precipitate;
(5) washing the rare earth composite hydroxide precipitate obtained in the step (4) to remove impurities, dispersing the precipitate in a solvent again, adding a structure regulator at 25-70 ℃, and continuously stirring for 30-60 min to obtain rare earth composite hydroxide slurry;
(6) filtering and drying the rare earth composite hydroxide slurry obtained in the step (5), roasting at 700 ℃ for 4h, and crushing to obtain a rare earth composite oxide;
the structure regulator in the step (5) is at least one of a beta-diketone compound, a fatty amine and a fatty acid; the beta-diketone compound is at least one of stearoylbenzoylmethane, ethyl acetylacetonate, 4, 6-dioxoheptanoic acid, di-tert-valerylmethane, 2, 4-octanedione and dibenzoylmethane; the fatty acid is at least one of caprylic acid, pelargonic acid, capric acid, lauric acid, stearic acid, oleic acid and citric acid; the fatty amine is at least one of lauryl amine, oleyl amine, trioctyl decyl tertiary amine, n-decyl amine, tetramethyl ammonium hydroxide and hexadecyl trimethyl ammonium hydroxide; the structural regulator accounts for 20-50% of the weight of the rare earth composite oxide.
2. The method for producing a rare earth composite oxide according to claim 1, wherein the rare earth oxide other than ceria is at least one of yttria, lanthana, praseodymia, and neodymia; the transition metal in the transition metal oxide is at least one of niobium, manganese, iron, cobalt, nickel and copper.
3. The method for producing a rare earth composite oxide as claimed in claim 1, wherein the zirconium salt in the zirconium salt solution in the step (1) is zirconium oxychloride or zirconium nitrate.
4. The method for producing a rare earth composite oxide according to claim 1, wherein the sulfate in the step (1) is at least one of zirconium sulfate, sodium sulfate and potassium sulfate.
5. The method for producing a rare earth composite oxide according to claim 1, wherein the sulfate in the sulfate solution in the step (2) is at least one of sodium sulfate and potassium sulfate; sulfate radical accounts for 12-46% of the weight of the zirconium dioxide; the mass fraction of sulfate in the sulfate solution is 5-20 wt%.
6. The method for producing a rare earth composite oxide as claimed in claim 1, wherein the rare earth salt and the transition metal salt in the rare earth salt solution and the transition metal salt solution in the step (3) are chloride salts or nitrate salts; the mass fraction of the rare earth salt and the transition metal salt in the rare earth salt solution and the transition metal salt solution is 10-30 wt%.
7. The method for producing a rare earth composite oxide according to claim 1, wherein the alkali in the alkali solution in the step (4) is at least one of sodium hydroxide, potassium hydroxide and lithium hydroxide; the mass fraction of alkali in the alkali solution is 10-30 wt%.
8. The method for producing a rare earth composite oxide according to claim 1, wherein the solvent in the step (5) is at least one of water and ethanol.
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