CN111392759A - Preparation method of high-stability high-oxygen-storage cerium-zirconium solid solution - Google Patents

Preparation method of high-stability high-oxygen-storage cerium-zirconium solid solution Download PDF

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CN111392759A
CN111392759A CN202010327731.2A CN202010327731A CN111392759A CN 111392759 A CN111392759 A CN 111392759A CN 202010327731 A CN202010327731 A CN 202010327731A CN 111392759 A CN111392759 A CN 111392759A
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oxygen
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zirconium
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黄贻展
徐清辉
王�忠
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Zibo Jiahua New Material Co ltd
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Zibo Zamr New Material Resource Co ltd
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    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/02—Oxides
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    • C01—INORGANIC CHEMISTRY
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Abstract

The invention relates to a preparation method of a high-stability high-oxygen-storage cerium-zirconium solid solution, which belongs to the technical field of cerium-zirconium solid solutions and comprises the following steps of (a) preparing an acid solution containing a compound of cerium and zirconium, (b) preparing an acid solution of a compound of W, (c) adding the acid solution formed in the step (b) into the acid solution formed in the step (a) to form a mixed solution, (d) preparing an alkaline solution with the concentration of 3-6 mo/L, (e) adding a surfactant into the alkaline solution prepared in the step (d) to obtain a mixed solution, (f) adjusting the pH of the acid solution prepared in the step (c) by using the mixed solution prepared in the step (e), and (g) separating, washing, filtering and calcining a precipitate formed in the step (f) to obtain a product.

Description

Preparation method of high-stability high-oxygen-storage cerium-zirconium solid solution
Technical Field
The invention relates to a preparation method of a cerium-zirconium solid solution with high stability and high oxygen storage capacity, belonging to the technical field of cerium-zirconium solid solutions.
Background
The tail gas of motor vehicle is the main pollution of the current atmosphere, and the exhausted HC, CO and NOxDirectly harms human health and causes harm to the environment. The most effective method for treating the motor vehicle tail gas pollutants is to adopt an external purification catalyst, such as a three-way catalyst. The oxygen storage material is one of the key materials of the automobile exhaust purification three-way catalystThe performance and service life of the catalyst are determined. Early research on oxygen storage materials was primarily directed to cerium-based oxygen storage materials, such as CeO2、CeO2-ZrO2Solid solution. Research shows that the addition of rare earth, alkaline earth and transition metal plasma can improve CeO2Thermal stability and redox ability. Among them, there are reports on Zr removal4+Besides, L a3+、Pr4+、Hf4+、Tb4+、Fe3+、Ti4+And Sn4+Equal non-noble metal doped with CeO2And (4) carrying out modification.
Besides the modification by means of doping metal ions, the components of the oxygen storage material also undergo a process of coordinated development from a single component to multiple components, so as to further improve the oxygen storage capacity, the thermal stability and the high-temperature oxidation resistance. Removing binary CeO2-ZrO2、CeO2-TiO2、CeO2-SiO2CeO appeared in addition to the oxygen storage material2-ZrO2-Y2O3、CeO2-ZrO2-La2O3、CeO2-ZrO2-L nOx (L n ═ Tb, Nd, Sr, Sc), and Ce0.55Zr0.35Y0.05La0.05O2And the research reports of the quaternary oxygen storage material.
Cerium oxide in cerium zirconium solid solutions has valence state variability and Ce occurs in oxidizing or reducing atmospheres4+And Ce3+The cerium-zirconium solid solution has the function of storing and discharging oxygen, the air-fuel ratio window of the catalyst can be effectively widened, and the catalytic purification performance of the automobile exhaust catalyst is greatly improved. The cerium-zirconium solid solution is applied to an automobile exhaust catalyst, and is required to bear higher degradation temperature of exhaust and maintain the stability of the structure and performance of the material. Therefore, the cerium-zirconium solid solution with high specific surface and excellent performance is widely applied to the automobile exhaust purification catalyst at present, and becomes an irreplaceable key material of the automobile exhaust purification catalyst. For catalysts prepared with cerium zirconium solid solutions, a high specific surface is very necessary. However, under the high temperature action of automobile exhaust, the ratio of cerium-zirconium solid solutionThe surface is degraded and the performance is deteriorated. In order to adapt to more strict motor vehicle exhaust emission standards, the development of cerium-zirconium solid solutions with high specific surface area, high stability and high oxygen storage capacity is a necessary trend.
CN20191023888300 discloses a preparation method of a cerium-zirconium solid solution with high oxygen storage capacity, which comprises the following steps: (a) preparing an acidic solution of a cerium-containing compound; (b) preparing an acidic solution comprising a compound of cerium and zirconium; (c) adjusting the concentration and temperature of the acidic solution prepared in step (b); (d) preparing an alkaline solution; (e) adding an additive into the alkaline solution to obtain a mixed solution; (f) adjusting the pH of the solution in the step (c) by using the mixed solution in the step (e); (g) adjusting the pH of the solution of step (a) with the solution of step (f); (h) separating, washing, filtering and calcining to obtain the solid solution product. The cerium-zirconium solid solution prepared by the method has good stability, large specific surface area and high oxygen storage capacity. However, the manufacturing process is complex, the production period is long, and the difficulty is increased for production control.
Disclosure of Invention
The invention aims to provide a preparation method of a high-stability high-oxygen-storage cerium-zirconium solid solution, which has scientific and reasonable design, simplicity and feasibility and low production cost, and the prepared cerium-zirconium solid solution not only has high specific surface and high oxygen storage capacity, but also has high stability and remarkable economic benefit.
The preparation method of the high-stability high-oxygen-storage cerium-zirconium solid solution comprises the following steps:
(a) preparing an acidic solution containing a compound of cerium and zirconium, wherein the cerium content is 20-45 wt%, the zirconium content is 35-65 wt%, and the other component is one or more of L a, Y, Nd or Pr, the content being 5-15 wt%;
(b) preparing an acidic solution of the compound of W;
(c) adding the acid solution formed in the step (b) into the acid solution formed in the step (a) to form a mixed solution, wherein the content of W is 0.1-3 wt%, water is added to adjust the concentration to be 100-200 g/L, and the temperature is adjusted to be 20-50 ℃;
(d) preparing alkaline solution with the concentration of 3-6 mo/L, and adjusting the temperature to 20-50 ℃;
(e) adding a surfactant into the alkaline solution prepared in the step (d) to obtain a mixed solution;
(f) adjusting the pH of the acidic solution prepared in the step (c) to be more than 8.5 by using the mixed solution prepared in the step (e), wherein the adjusting time is not less than 1 hour;
(g) separating the precipitate formed in step (f), washing, filtering and calcining to obtain the product.
In step (a), the compound containing cerium and zirconium is a nitrate, sulfate or chloride.
In step (b), the compound of W is a nitrate, sulfate, acetate, oxalate or chloride.
In step (d), the alkaline solution is NH4OH, KOH, NaOH or NH4HCO3One or more of them.
In the step (e), the surfactant is added in an amount of 10 to 50 wt% of the mass of all the compound components in the step (a) and the step (b) when converted to oxides.
The surfactant is one or more of butyl carbitol, carboxylic acid and its salt or carboxymethylated fatty alcohol ethoxylate.
In step (g), the precipitate is washed with water to a conductivity of 10-50 ms/cm.
In step (g), filtering until the water content of the precipitate is 70-90 wt%.
In the step (g), the calcination temperature is 700-900 ℃, and the calcination time is 4-8 h.
In the invention, tungsten is doped, the tungsten belongs to an element in a sixth subgroup, molybdenum and tungsten belong to the same group element, although the properties of the same group element have certain similarity theoretically, the molybdenum and the tungsten are not absolute, the tungsten is mainly hexavalent cation in nature, and the ionic radius of the tungsten is 0.68 × 10-10And m is selected. Due to W6+Small ion radius, high electrovalence, strong polarization ability and easy formation of complex anion. Molybdenum is a transition element, is easy to change the oxidation state of the molybdenum, and plays a role in transferring electrons in the in vivo oxidation-reduction reaction. In the oxidized form, molybdenum is likely to be in the +6 state. Although it is also likely to be reduced to the +5 valence state first during electron transfer. However, molybdenum has also been found in reduced enzymesOther oxidation states of (a). Since the valence shell orbitals are in a half-filled state, molybdenum is between the lithophilic element (8 electron-ion configuration) and the copphilic element (18 electron-ion configuration), representing a typical transition state. In the invention, doping experiments are carried out on molybdenum and tungsten, OSC data show that the SA of the solid solution is reduced by doping the molybdenum, the OSC is not obviously changed, and the doping of the tungsten is beneficial to improving the OSC of the solid solution.
The specific surface area of the molybdenum-doped cerium-zirconium solid solution is 71.62m2The oxygen storage amount is 887 mu mol/g; meanwhile, the obtained solid solution was aged at 1000 ℃ for 10 hours and then tested to have a specific surface area of 35.71m2The oxygen storage amount is 792 mu mol/g; the oxygen storage capacity of the resulting solid solution was determined to be 707. mu. mol/g after aging at 1100 ℃ for 10 hours. The OSC result is not ideal.
Compared with the prior art, the invention has the following beneficial effects:
(1) the solid solution according to the invention is based on zirconium oxide and cerium oxide and is characterized in that it has a cerium oxide proportion of not more than 50 wt.%, at least 30m after calcination at 1000 ℃ for 10 hours2A specific surface area per gram and an oxygen storage capacity of at least 1000. mu. mol/g after calcination at 800 ℃ in air for 5 hours;
(2) the invention also relates to solid solutions based on zirconium oxide and cerium oxide, having the same proportions and the same surface characteristics as those given above and an oxygen storage capacity of at least 900 [ mu ] mol/g after calcination in air at 1000 ℃ for 10 hours;
(3) the invention also relates to solid solutions based on zirconia and ceria having the same proportions and the same surface characteristics as those given above and an oxygen storage capacity of at least 800 [ mu ] mol/g after calcination in air at 1100 ℃ for 10 hours;
(4) the invention has scientific and reasonable design, simple and easy operation and low production cost, reduces the manufacturing steps, shortens the production period, ensures that the production process is easy to control and has obvious economic benefit.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.
The raw materials used in the examples were all commercially available raw materials except for those specifically mentioned.
Example 1
A preparation method of a high-stability high-oxygen-storage cerium-zirconium solid solution comprises the following steps:
(a) firstly, batching according to the mass ratio of Ce/Zr/L a/Nd oxide 20/65/5/5 to obtain an acid solution of ammonium ceric nitrate, zirconium oxychloride, lanthanum nitrate and yttrium nitrate;
(b) preparing an acidic solution of ammonium paratungstate;
(c) adding the acidic solution formed in the step (b) into the acidic solution formed in the step (a) to form a mixed solution, wherein the oxide content of W is 0.15%, diluting the solution to the concentration of 180 g/L by using water, and adjusting the temperature to 40 ℃;
(d) preparation of 3.5 mol/L NH4OH and NH4HCO3Mixed solution (NH)4OH/NH4HCO310/1) and adjusting the temperature to 25 ℃;
(e) adding lauric acid (the addition amount is 35 wt% of the mass of all the compound components converted into oxides in the step (a) and the step (b)) into the alkaline solution prepared in the step (d), and obtaining a mixed solution after clearing;
(f) adding the solution prepared in the step (c) into the solution prepared in the step (e) at a constant speed for the following time: 1h, obtain a precipitate slurry with a final pH of 9.2;
(g) the precipitate slurry was subjected to solid-liquid separation and the filter cake was washed to conductivity: 10ms/cm, and the water content of the final filter cake is 75 percent; and calcining the filter cake at 850 ℃ for 6h to obtain the high-stability high-oxygen-storage cerium-zirconium solid solution.
The specific surface area of the obtained cerium-zirconium solid solution is 67m2The oxygen storage amount is 1028 mu mol/g; meanwhile, the obtained solid solution was aged at 1000 ℃ for 10 hours and then tested to have a specific surface area of 46m2The oxygen storage amount is 922 mu mol/g; the oxygen storage capacity of the resulting solid solution was measured to be 809. mu. mol/g after aging at 1100 ℃ for 10 hours.
Example 2
A preparation method of a high-stability high-oxygen-storage cerium-zirconium solid solution comprises the following steps:
(a) firstly, batching according to the mass ratio 45/45/8/2 of Ce/Zr/L a/Pr oxide to obtain an acidic solution of ammonium ceric nitrate, zirconium nitrate, lanthanum nitrate and praseodymium nitrate;
(b) preparing an acidic solution of ammonium paratungstate;
(c) adding the solution (b) to the solution (a) to form a mixed solution, wherein the oxide content of W is 0.2%, diluting the solution with water to a concentration of 110 g/L, and adjusting the temperature to 35 ℃;
(d) preparation of 5.5 mol/L NH4Mixed solution of OH and NaOH (NH)4OH/NaOH 10/1 mole ratio) solution and temperature was adjusted to 35 ℃;
(e) adding lauric acid (the addition amount is 50 wt% of the mass of all the compound components converted into oxides in the step (a) and the step (b)) into the alkaline solution prepared in the step (d), and obtaining a mixed solution after clearing;
(f) adding the solution prepared in the step (c) into the solution prepared in the step (e) at a constant speed for the following time: 1h, obtain a precipitate slurry with a final pH of 9.6;
(g) the precipitate slurry was subjected to solid-liquid separation and the filter cake was washed to conductivity: 25ms/cm, and the water content of the final filter cake is 80%; and calcining the filter cake at 800 ℃ for 5h to obtain the high-stability high-oxygen-storage cerium-zirconium solid solution.
Specific surface area of the obtained cerium-zirconium solid solution is 81.89m2The oxygen storage amount is 1134 mu mol/g; meanwhile, the obtained solid solution is aged at 1000 ℃ for 10 hours, and the specific surface area is tested to be 37m2Per gram, the tested oxygen storage amount is 1071 mu mol/g; the oxygen storage capacity of the resulting solid solution was measured to be 919. mu. mol/g after aging at 1100 ℃ for 10 hours.
Example 3
A preparation method of a high-stability high-oxygen-storage cerium-zirconium solid solution comprises the following steps:
(a) firstly, batching according to the mass ratio 45/45/5/5 of Ce/Zr/L a/Y oxide to obtain an acid solution of ammonium ceric nitrate, zirconium nitrate, lanthanum nitrate and neodymium nitrate;
(b) preparing an acidic solution of ammonium paratungstate;
(c) adding the solution (b) to the solution (a) to form a mixed solution, wherein the oxide content of W is 1.5%, diluting the solution with water to a concentration of 150 g/L, and adjusting the temperature to 25 ℃;
(d) 4.5 mol/L NH is prepared4OH solution, and adjusting the temperature to 40 ℃;
(e) to NH4Adding 10 wt% of butyl carbitol into the OH solution, uniformly mixing, adding 30 wt% of lauric acid, and dissolving to obtain a mixed solution; the addition amount is based on the mass of all the compound components converted into oxides in the step (a) and the step (b);
(f) adding the solution prepared in the step (c) into the solution prepared in the step (e) at a constant speed for the following time: 1h, obtain a precipitate slurry with a final pH of 9.7;
(g) the precipitate slurry was subjected to solid-liquid separation and the filter cake was washed to conductivity: 25ms/cm, and the water content of the final filter cake is 85%; and calcining the filter cake at 750 ℃ for 6h to obtain the high-stability high-oxygen-storage cerium-zirconium solid solution.
The specific surface area of the obtained cerium-zirconium solid solution is 72m2The oxygen storage amount is 1063 mu mol/g; meanwhile, the obtained solid solution is aged at 1000 ℃ for 10 hours, and the specific surface area is tested to be 35m2The oxygen storage amount is 980 mu mol/g; the oxygen storage capacity of the resulting solid solution was measured to be 847. mu. mol/g after aging at 1100 ℃ for 10 hours.
Comparative example 1
A preparation method of a high-stability high-oxygen-storage cerium-zirconium solid solution comprises the following steps:
(a) firstly, batching according to the mass ratio of the Ce/Zr/L a/Y oxide of 25/65/4/6 to obtain an acid solution of ammonium ceric nitrate, zirconium nitrate, lanthanum nitrate and neodymium nitrate;
(b) preparing an acidic solution of ammonium paramolybdate;
(c) adding the solution (b) into the solution (a) to form a mixed solution, wherein the oxide content of Mo is 0.3%, diluting the solution to the concentration of 180 g/L by using water, and adjusting the temperature to 40 ℃;
(d) preparation of 3.5 mol/L NH4OH and NH4HCO3Mixed solution (NH)4OH/NH4HCO310/1) and adjusting the temperature to 25 ℃;
(e) adding lauric acid (the addition amount is 35 wt% of the mass of all the compound components converted into oxides in the step (a) and the step (b)) into the alkaline solution prepared in the step (d), and obtaining a mixed solution after clearing;
(f) adding the solution prepared in the step (c) into the solution prepared in the step (e) at a constant speed for the following time: 1h, obtain a precipitate slurry with a final pH of 9.2;
(g) the precipitate slurry was subjected to solid-liquid separation and the filter cake was washed to conductivity: 10ms/cm, and the water content of the final filter cake is 75 percent; and calcining the filter cake at 850 ℃ for 6h to obtain the high-stability high-oxygen-storage cerium-zirconium solid solution.
The specific surface area of the obtained molybdenum-doped cerium-zirconium solid solution is 71.62m2The oxygen storage amount is 887 mu mol/g; meanwhile, the obtained solid solution was aged at 1000 ℃ for 10 hours and then tested to have a specific surface area of 35.71m2The oxygen storage amount is 792 mu mol/g; the oxygen storage capacity of the resulting solid solution was determined to be 707. mu. mol/g after aging at 1100 ℃ for 10 hours. The OSC result is not ideal.

Claims (9)

1. A preparation method of a high-stability high-oxygen-storage cerium-zirconium solid solution is characterized by comprising the following steps: the method comprises the following steps:
(a) preparing an acidic solution containing a compound of cerium and zirconium, wherein the cerium content is 20-45 wt%, the zirconium content is 35-65 wt%, and the other component is one or more of L a, Y, Nd or Pr, the content being 5-15 wt%;
(b) preparing an acidic solution of the compound of W;
(c) adding the acid solution formed in the step (b) into the acid solution formed in the step (a) to form a mixed solution, wherein the content of W is 0.1-3 wt%, water is added to adjust the concentration to be 100-200 g/L, and the temperature is adjusted to be 20-50 ℃;
(d) preparing alkaline solution with the concentration of 3-6 mo/L, and adjusting the temperature to 20-50 ℃;
(e) adding a surfactant into the alkaline solution prepared in the step (d) to obtain a mixed solution;
(f) adjusting the pH of the acidic solution prepared in the step (c) to be more than 8.5 by using the mixed solution prepared in the step (e), wherein the adjusting time is not less than 1 hour;
(g) separating the precipitate formed in step (f), washing, filtering and calcining to obtain the product.
2. The method for preparing a highly stable and oxygen-storing cerium-zirconium solid solution according to claim 1, wherein: in step (a), the compound containing cerium and zirconium is a nitrate, sulfate or chloride.
3. The method for preparing a highly stable and oxygen-storing cerium-zirconium solid solution according to claim 1, wherein: in step (b), the compound of W is a nitrate, sulfate, acetate, oxalate or chloride.
4. The method for preparing a highly stable and oxygen-storing cerium-zirconium solid solution according to claim 1, wherein: in step (d), the alkaline solution is NH4OH, KOH, NaOH or NH4HCO3One or more of them.
5. The method for preparing a highly stable and oxygen-storing cerium-zirconium solid solution according to claim 1, wherein: in the step (e), the surfactant is added in an amount of 10 to 50 wt% of the mass of all the compound components in the step (a) and the step (b) when converted to oxides.
6. The method for preparing a highly stable and oxygen-storing cerium-zirconium solid solution according to claim 1, wherein: the surfactant is one or more of butyl carbitol, carboxylic acid and its salt or carboxymethylated fatty alcohol ethoxylate.
7. The method for preparing a highly stable and oxygen-storing cerium-zirconium solid solution according to claim 1, wherein: in step (g), the precipitate is washed with water to a conductivity of 10-50 ms/cm.
8. The method for preparing a highly stable and oxygen-storing cerium-zirconium solid solution according to claim 1, wherein: in step (g), filtering until the water content of the precipitate is 70-90 wt%.
9. The method for preparing a highly stable and oxygen-storing cerium-zirconium solid solution according to claim 1, wherein: in the step (g), the calcination temperature is 700-900 ℃, and the calcination time is 4-8 h.
CN202010327731.2A 2020-04-23 2020-04-23 Preparation method of high-stability high-oxygen-storage cerium-zirconium solid solution Withdrawn CN111392759A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022034373A1 (en) * 2020-08-12 2022-02-17 Neo Performance Materials (Singapore) Pte. Ltd. Oxygen storage capacity enhanced compositions

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022034373A1 (en) * 2020-08-12 2022-02-17 Neo Performance Materials (Singapore) Pte. Ltd. Oxygen storage capacity enhanced compositions

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