CN117509724A - Cerium-zirconium composite oxide and preparation method thereof - Google Patents

Cerium-zirconium composite oxide and preparation method thereof Download PDF

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CN117509724A
CN117509724A CN202311272265.2A CN202311272265A CN117509724A CN 117509724 A CN117509724 A CN 117509724A CN 202311272265 A CN202311272265 A CN 202311272265A CN 117509724 A CN117509724 A CN 117509724A
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cerium
soluble
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zirconium
solution
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CN117509724B (en
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陈贤娜
黄英强
谭程校
高彬
万国江
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Jiangmen Kanhoo Industry Co ltd
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Abstract

The invention belongs to the field of catalysts, and discloses a preparation method of a cerium-zirconium composite oxide, which comprises the following steps: step 1: adding hydrogen peroxide into an aqueous solution containing soluble cerium salt, soluble zirconium salt and soluble doped metal salt; step 2: adding the solution obtained in the step 1 into a precipitator, controlling the pH of the solution to be 8-10, controlling the temperature of the solution to be 50-80 ℃ after the solution obtained in the step 1 is added, and stirring for 1-8 hours to enable metal ions in the soluble cerium salt, the soluble zirconium salt and the soluble doped metal salt to react with the precipitator to form metal salt precipitate; step 3: separating the metal salt precipitate from the solution, washing and drying, and roasting at 700-900 ℃ for 3-5 h. The method optimizes the specific surface area of fresh crystal grain bodies and reduces the specific surface area of the crystal grain bodies after aging as little as possible by controlling rare earth doping and temperature-controlled precipitation, and simultaneously controls the increase of the crystal grains. Meanwhile, the invention also provides a cerium-zirconium composite oxide.

Description

Cerium-zirconium composite oxide and preparation method thereof
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a cerium-zirconium composite oxide and a preparation method thereof.
Background
The problem of the greenhouse effect is increasingly prominent at present, automobile exhaust is one of the main factors of atmospheric environmental pollution, the number of motor vehicles is greatly increased, the ratio of the oil vehicle to new energy is approximately 9:1, and the problem of automobile exhaust emission still needs to be solved.
The ternary catalytic device is one of effective measures for catalytic purification of automobile exhaust, and can reduce the contents of three toxic gases of HC, CO and NOx in the exhaust. Wherein, the catalyst takes part in the catalytic reaction is a layer of noble metals such as platinum, rhodium, palladium and the like and CeO-containing coating as rare earth coating covered on the porous ceramic carrier 2 Catalytic auxiliary (oxygen storage material). The physical and chemical properties of the oxygen storage material directly influence the dispersion and stability of noble metals, thereby influencing the catalytic effect.
The existing preparation method of the oxygen storage material mainly comprises one or two or more of coprecipitation method, ball milling method, hydrothermal method and spray precipitation, wherein the coprecipitation method is relatively simple and convenient, and is more beneficial to popularization and industrialization.
Prior art 1: CN103566923B discloses a cerium-zirconium-aluminum composite oxide oxygen storage material and a preparation method thereof, and the specific method comprises the following steps: 114.3g of pseudo-boehmite with the alumina content of 70 percent is added into 216.0g of deionized water, 30.0g of Tween 80 is added, and the mixture is heated and stirred for 1h in a water bath with the temperature of 90 ℃; dissolving 25.6g of cerium nitrate and 30.3g of zirconium nitrate with 200g of deionized water, adding 26.4g of hydrogen peroxide (15 wt%) and fully oxidizing, then adding into the above-mentioned solution, and preserving heat for 1h; ammonia water with the concentration of 25wt percent is added, the pH of the end point is controlled to be 10, and the temperature is kept for 1h. And then stopping stirring, aging for 3 hours at 90 ℃, filtering to obtain a precipitate, washing with water to be neutral, adding 50g of polyethylene glycol 400 into a filter cake, pulping and dispersing, placing in a muffle furnace, roasting for 3 hours at 550 ℃, and obtaining the cerium-zirconium-aluminum composite oxide oxygen storage material at a heating rate of 2 ℃/min.
The fresh specific surface area of the material is 240m 2 Per g, pore volume of 0.70cm 3 /g, average pore size 5nm; the specific surface area after roasting at 1000 ℃ for 4 hours is 136m 2 Per g, pore volume of 0.50cm 3 And/g, the average pore diameter is 13nm.
The proposal introduces pseudo-boehmite to increase the surface area and pore volume of the product, so that the specific surface area is not obviously reduced after the product is aged and calcined.
The prior art 2:CN105771955A discloses a preparation method of cerium-zirconium solid solution, which comprises the following specific scheme: 1. respectively dissolving cerium carbonate, zirconium carbonate, lanthanum carbonate and praseodymium carbonate in concentrated nitric acid to obtain a cerium nitrate solution, a zirconium nitrate solution, a lanthanum nitrate solution and a praseodymium nitrate solution with the concentration of 1.5mol/L, wherein the cerium nitrate solution and the zirconium nitrate solution are mixed according to the mass ratio of cerium oxide to zirconium oxide of 0.4:0.5, mixing, wherein the addition amount of the lanthanum nitrate solution is 5.56% of the total mass of cerium-zirconium oxide calculated by lanthanum oxide, the addition amount of the praseodymium nitrate solution is 5.56% of the total mass of cerium-zirconium oxide calculated by praseodymium oxide, and adding water to dilute to a mass concentration of 100mg/mL calculated by total oxide to obtain a mixed salt solution;
2. adding hydrogen peroxide to the mixed salt solution, wherein the dosage of the hydrogen peroxide is 1 time of the molar quantity of cerium ions, and uniformly stirring to obtain acid liquor A;
3. preparing a solution with the concentration of 1mol/L by using a precipitator sodium hydroxide, adding a surfactant sodium dodecyl sulfate, wherein the dosage of the surfactant is 1 time of the mass of the cerium-zirconium solid solution, uniformly stirring to obtain an alkali liquor B, and dividing the alkali liquor B into two parts;
4. dropwise adding one part of alkali liquor B into the acid liquor A until the pH value is 6-8, adding the other part of alkali liquor B, continuously dropwise adding the acid liquor A, and controlling the final pH value to be 9-10 to obtain a precipitate;
5. the precipitate is aged, washed, roasted and screened by a pair of rollers, wherein the ageing temperature is 30 ℃, the time is 1h, the precipitate is washed by water until the conductivity of the washing liquid is less than 10mS/cm, the roasting temperature is 780 ℃, and the time is 6h, so as to obtain the cerium-zirconium solid solution.
Its fresh specific surface area is 83m 2 Per gram, specific surface area after aging of 42m 2 /g。
The scheme adopts a swing precipitation method to reduce the reduction amplitude of the specific surface area after aging.
Prior art 3: CN107952424a discloses a preparation method of nano cerium zirconium solid solution, which comprises the following specific scheme: the method comprises the following steps:
(1) Preparing a solution A: preparing a mixed solution containing zirconium nitrate, cerium nitrate, lanthanum nitrate and yttrium nitrate, namely a solution A;
(2) Preparing a solution B: preparing a solution containing ionic membrane liquid alkali, namely a solution B;
(3) Placing pure water, ionic membrane liquid alkali and a surfactant into a reactor, and carrying out heat preservation and stirring at 70-80 ℃ to dissolve; simultaneously adding the solution A and the solution B; adding hydrogen peroxide, and continuing to keep the temperature and stir for 15-45min; heating to 90-100 ℃, and reacting for 3-5h at a temperature; filtering to obtain wet cake;
(4) And (3) washing a filter cake: pulping wet cake and ammonium citrate in pure water, adjusting pH to 9-10 with strong ammonia water, maintaining at 65-75deg.C for 0.5-1.5 hr, and hot filtering to obtain wet cake; repeating the washing for 3-5 times;
(5) Placing the wet cake into a trolley resistance furnace, heating to 750 ℃ at a heating rate of 1.5 ℃/min, stopping, taking out the powder, and crushing the powder by using a ball mill.
Comparative example 1 of this case also describes that alkali solution and hydrogen peroxide are used to add metal salt at 75 ℃, and the temperature is kept at 95 ℃ for 4 hours;
in example 1 and comparative example 1 of this case, the process was different in the case of the same ratio of raw materials, and the change in specific surface area after aging was not large, but the oxygen storage amount of the cerium-zirconium solid solution was reduced by about 25%.
It is explained that the specific surface area after aging cannot be improved by adopting the ionic membrane liquid alkali, and the oxygen storage amount can be effectively improved.
Prior art 4: CN107138146B discloses a preparation method of mesoporous cerium zirconium solid solution, which comprises the following specific scheme:
227g ZrOCl were added 2 Hydrated crystal (ZrOCl) 2 53.34 wt%) was dissolved in 2515g of water, after which 114. 114g H was added 2 SO 4 And 20g of P123 solution (H 2 SO 4 25.6 wt%) was added thereto, at which point the pH of the solution was less than 0.5.ZrOCl 2 Slow self-hydrolysis at 55deg.C, slowly adding ammonia water (14.5% NH) into the slurry 3 ·H 2 O) until pH 7.5. After the pH adjustment was completed, the slurry was aged at 55℃for 0.5 hours to obtain a slurry containing the target zirconia. And pulping, washing and filtering the target zirconia for multiple times to obtain a zirconia precursor.
60g Ce (NO) 3 ) 3 ·6H 2 O was dissolved in 2000ml of water to prepare Ce (NO) 3 ) 3 A solution. Adding the zirconia precursor to Ce (NO) 3 ) 3 In solution. The zirconia was stirred at 35 ℃ for 0.5h to uniformly disperse the zirconia in the solution. Ammonia was then added dropwise to adjust the pH to 9.5. After the pH adjustment was completed, the mixture was aged at 67℃for 5min. Then 100ml of hydrogen peroxide solution (5.3% H) was slowly added thereto 2 O 2 ) And aging for 30min to obtain the target cerium-zirconium compound. The target cerium zirconium complex was pulped, washed and filtered twice. During the beating, the pH was adjusted to 10.3, and the ammonia water consumed per beating was about 100ml. In the last filtration wash, it is necessary to reheat the water rinse until the pH is near neutral. And drying the washed filter cake in a 90 ℃ oven for 12 hours, and crushing the cerium-zirconium compound after drying to obtain the cerium-zirconium solid solution precursor.
Precursor of cerium-zirconium solid solutionThe body is placed at 600 ℃ for roasting for 3 hours, the heating speed is 2 ℃/min, and the specific surface area of the target cerium-zirconium solid solution is 213m 2 And/g. Roasting cerium-zirconium solid solution at 1000 deg.c for 4 hr at 5 deg.c/min to obtain sample with specific surface area of 34m 2 /g。
The decrease of the aging specific surface area of the cerium-zirconium solid solution is a very headache problem in the art as seen in prior art 4.
The above-mentioned prior arts 1 to 3 improve specific surface area after aging by various means.
Therefore, the problem solved by the present project is: how to improve the specific surface area after aging by other means.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of cerium-zirconium composite oxide, which aims to optimize the specific surface area of fresh crystals and reduce the specific surface area of the crystals after aging as little as possible and simultaneously control the increase of crystal grains by controlling rare earth doping and temperature-controlled precipitation.
Meanwhile, the invention also provides a cerium-zirconium composite oxide.
In order to achieve the aim of the invention, the invention adopts the following technical scheme: a preparation method of cerium-zirconium composite oxide comprises the following steps:
step 1: adding hydrogen peroxide into an aqueous solution containing soluble cerium salt, soluble zirconium salt and soluble doped metal salt;
step 2: adding the solution obtained in the step 1 into a precipitator, controlling the pH of the solution to be 8-10, controlling the temperature of the solution to be 50-80 ℃ after the solution obtained in the step 1 is added, and stirring for 1-8 hours to enable metal ions in the soluble cerium salt, the soluble zirconium salt and the soluble doped metal salt to react with the precipitator to form metal salt precipitate;
step 3: separating the metal salt precipitate from the solution, washing and drying, and roasting at 700-900 ℃ for 3-5h;
the metal elements in the soluble doped metal salt comprise rare earth elements, wherein the rare earth elements are one or more of La, Y, pr, nd and Tb;
the mole ratio of cerium, zirconium and rare earth elements in the soluble cerium salt, the soluble zirconium salt and the soluble doped metal salt is 20-60: 30-70: 5 to 15.
In the above-mentioned preparation method of the cerium-zirconium composite oxide, the temperature at the time of precipitation in the step 2 is 55 to 70 ℃.
In the above preparation method of the cerium-zirconium composite oxide, anions of the soluble cerium salt, the soluble zirconium salt and the soluble doped metal salt are each independently chloride ion, nitrate ion, oxychloride ion or sulfate ion.
In the above preparation method of the cerium-zirconium composite oxide, in the step 1, the total concentration of metal ions in the soluble cerium salt, the soluble zirconium salt and the soluble doped metal salt is 50-200mg/ml.
In the preparation method of the cerium-zirconium composite oxide, the molar ratio of the addition amount of the hydrogen peroxide to the cerium element is 1:1-1:3.
In the preparation method of the cerium-zirconium composite oxide, the molar ratio of the addition amount of the hydrogen peroxide to the cerium element is 1:1.8-1:2.
In the preparation method of the cerium-zirconium composite oxide, the precipitant is one or more of ammonia water, ammonium carbonate and ammonium bicarbonate; the precipitant is 1.2 times or more of the total equivalent of metal ions in the soluble cerium salt, the soluble zirconium salt and the soluble doped metal salt.
In the above preparation method of the cerium-zirconium composite oxide, the metal element in the soluble doped metal salt comprises an alkaline earth metal element, and the alkaline earth metal element is one or more of Ca, sr, ba and Mg; the molar ratio of cerium, zirconium, rare earth elements and alkaline earth elements is 20-60: 30-70: 5-15: 0.1 to 5.
Finally, the invention also discloses a cerium-zirconium composite oxide which is prepared by adopting any one of the methods.
Compared with the prior art, the invention has the following beneficial effects:
the invention optimizes the specific surface area of fresh crystals and reduces the specific surface area of the aged crystals as little as possible by controlling rare earth doping and temperature-controlled precipitation, and simultaneously controls the increase of crystal grains;
as further optimization of the invention, the invention can further improve the aging performance of the crystal by further optimizing the precipitation temperature and doping alkaline earth metals.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
Step 1: mixing cerium chloride, zirconium oxychloride and lanthanum chloride, dissolving with deionized water, adding hydrogen peroxide, adding water to dilute until the total metal ions of cerium, zirconium and lanthanum have the weight of 150mg/ml, and uniformly stirring to obtain a mixed salt solution;
the molar ratio of cerium element, zirconium element and lanthanum element is as follows: 5:4:1;
the molar quantity of the hydrogen peroxide is 0.5 times of that of the cerium element;
step 2: diluting strong ammonia water (26%) to the same volume as the mixed metal ion solution;
step 3: adding the mixed salt solution into the step 2, stirring while adding, adjusting the ph of the solution to be 8, heating the solution to 60 ℃ by an oil bath after the mixed metal ion solution is added, and stirring for 8 hours;
step 4: washing the precipitate obtained in the step 3 with deionized water for 3 times, and carrying out suction filtration;
step 5: roasting the sample obtained in the step 4 for 4 hours at 720 ℃ in a resistance furnace;
step 6: crushing the baked sample to obtain cerium-zirconium composite oxide;
step 7: and (3) roasting the sample obtained in the step (6) for 10 hours at the temperature of 1100 ℃ in a resistance furnace to obtain an aged sample.
Example 2
Step 1: mixing cerium chloride, zirconium oxychloride and yttrium chloride, dissolving with deionized water, adding hydrogen peroxide, adding water to dilute until the total metal ion weight of cerium, zirconium and yttrium is 100mg/ml, and uniformly stirring to obtain a mixed salt solution;
the molar ratio of cerium element, zirconium element and yttrium element is as follows: 3:6:1;
the molar quantity of the hydrogen peroxide is 1 time of that of the cerium element;
step 2: diluting strong ammonia water (26%) to the same volume as the mixed metal ion solution;
step 3: adding the mixed salt solution into the step 2, stirring while adding, adjusting the ph of the solution to be 8, heating the solution to 70 ℃ by an oil bath after the mixed metal ion solution is added, and stirring for 8 hours;
step 4: washing the precipitate obtained in the step 3 with deionized water for 3 times, and carrying out suction filtration;
step 5: roasting the sample obtained in the step 4 for 3 hours at 900 ℃ in a resistance furnace;
step 6: crushing the baked sample to obtain cerium-zirconium composite oxide;
step 7: and (3) roasting the sample obtained in the step (6) for 10 hours at the temperature of 1100 ℃ in a resistance furnace to obtain an aged sample.
Example 3
Step 1: mixing cerium chloride, zirconium oxychloride and terbium chloride, dissolving with deionized water, adding hydrogen peroxide, adding water to dilute until the total metal ion weight of cerium, zirconium and terbium is 50mg/ml, and uniformly stirring to obtain a mixed salt solution;
the molar ratio of cerium element, zirconium element and terbium element is as follows: 2:7:1;
the molar quantity of the hydrogen peroxide is 1 time of that of the cerium element;
step 2: diluting strong ammonia water (26%) to the same volume as the mixed metal ion solution;
step 3: adding the mixed salt solution into the step 2, stirring while adding, adjusting the ph of the solution to be 10, heating the solution to 80 ℃ by an oil bath after the mixed metal ion solution is added, and stirring for 8 hours;
step 4: washing the precipitate obtained in the step 3 with deionized water for 3 times, and carrying out suction filtration;
step 5: roasting the sample obtained in the step 4 for 4 hours at 800 ℃ in a resistance furnace;
step 6: crushing the baked sample to obtain cerium-zirconium composite oxide;
step 7: and (3) roasting the sample obtained in the step (6) for 10 hours at the temperature of 1100 ℃ in a resistance furnace to obtain an aged sample.
Example 4
Step 1: mixing cerium chloride, zirconium oxychloride and terbium chloride, dissolving with deionized water, adding hydrogen peroxide, adding water to dilute until the total metal ion weight of cerium, zirconium and terbium is 200mg/ml, and uniformly stirring to obtain a mixed salt solution;
the molar ratio of cerium element, zirconium element and terbium element is as follows: 3.8:5.5:0.7;
the molar quantity of the hydrogen peroxide is 0.4 times of that of the cerium element;
step 2: diluting strong ammonia water (26%) to 0.5 times of the volume of the mixed metal ion solution;
step 3: adding the mixed salt solution into the step 2, stirring while adding, adjusting the ph=9 of the solution, and heating the solution to 50 ℃ by an oil bath after the mixed metal ion solution is added, and stirring for 8 hours;
step 4: washing the precipitate obtained in the step 3 with deionized water for 3 times, and carrying out suction filtration;
step 5: roasting the sample obtained in the step 4 for 5 hours at 700 ℃ in a resistance furnace;
step 6: crushing the baked sample to obtain cerium-zirconium composite oxide;
step 7: and (3) roasting the sample obtained in the step (6) for 10 hours at the temperature of 1100 ℃ in a resistance furnace to obtain an aged sample.
Example 5
Substantially as in example 1, except that the temperature of step 3 was 50 ℃.
Example 6
Substantially as in example 1, except that the temperature of step 3 was 70 ℃.
Example 7
Substantially as in example 1, except that the temperature of step 3 was 80 ℃.
Example 8
Step 1: mixing cerium chloride, zirconium oxychloride, lanthanum chloride and barium chloride, dissolving with deionized water, adding hydrogen peroxide, adding water to dilute until the total metal ions of cerium, zirconium, lanthanum and barium are 150mg/ml in weight, and uniformly stirring to obtain a mixed salt solution;
the molar ratio of cerium element, zirconium element, lanthanum element and barium element is as follows: 5:4:0.5:0.5;
the molar quantity of the hydrogen peroxide is 0.5 times of that of the cerium element;
step 2: diluting strong ammonia water (26%) to the same volume as the mixed metal ion solution;
step 3: adding the mixed salt solution into the step 2, stirring while adding, adjusting the ph of the solution to be 8, heating the solution to 60 ℃ by an oil bath after the mixed metal ion solution is added, and stirring for 8 hours;
step 4: washing the precipitate obtained in the step 3 with deionized water for 3 times, and carrying out suction filtration;
step 5: roasting the sample obtained in the step 4 for 4 hours at 720 ℃ in a resistance furnace;
step 6: crushing the baked sample to obtain cerium-zirconium composite oxide;
step 7: and (3) roasting the sample obtained in the step (6) for 10 hours at the temperature of 1100 ℃ in a resistance furnace to obtain an aged sample.
Example 9
Generally as in example 8, except that calcium chloride was used instead of barium chloride, the molar ratios of cerium element, zirconium element, lanthanum element, and calcium element were as follows: 4.8:4:1:0.2.
Example 10
Generally as in example 8, except that magnesium chloride was used instead of barium chloride, the molar ratios of cerium element, zirconium element, lanthanum element, and calcium element were as follows: 4.7:4:0.8:0.5.
Example 11
Substantially the same as in example 8, except that the temperature in step 3 was 50 ℃.
Example 12
Substantially as in example 8, except that the temperature of step 3 was 55 ℃.
Example 13
Substantially the same as in example 8, except that the temperature in step 3 was 70 ℃.
Example 14
Substantially the same as in example 8, except that the temperature in step 3 was 80 ℃.
Example 15
Generally, the molar amount of hydrogen peroxide was 1 time as much as that of cerium in example 8.
Example 16
Substantially the same as in example 8, except that the molar amount of hydrogen peroxide was 0.35 times the molar amount of cerium element.
Example 17
Substantially the same as in example 8, except that the molar amount of hydrogen peroxide was 0.7 times the molar amount of cerium element.
Comparative example 1
Substantially as in example 1, except that the temperature of step 3 was 85 ℃.
Comparative example 2
Substantially as in example 1, except that the temperature of step 3 was 90 ℃.
Comparative example 3
Substantially the same as in example 1, except that the mixing method of the salt and the aqueous ammonia in the step 3 is: ammonia was added dropwise to the mixed salt solution and adjusted to the same pH.
Comparative example 4
Generally as in example 1, the molar ratio of cerium element, zirconium element, lanthanum element is: 4:4:2.
Comparative example 5
Generally as in example 1, the molar ratio of cerium element, zirconium element, lanthanum element is: 5.4:4.5:0.1.
Performance testing
The test items include the specific surface area before burn-in and the grain test, and the specific surface area after burn-in and the grain test. The test results are shown in Table 1 below;
table 1 test results
Analysis of results:
1. it can be seen from examples 1 to 4 that the specific surface area and grain result of the crystal can be obtained satisfactorily by adopting rare earth doping and controlling the precipitation temperature, and the aged data has a remarkable effect improvement compared with comparative examples 1 and 2.
2. It can be seen from examples 1 and 5 to 7 that the specific surface area of the crystal and the grain result show a tendency of increasing and then decreasing with increasing temperature. The specific surface area and grain growth rate in the aging property also show a tendency of increasing and then decreasing.
3. It can be seen from examples 8 to 10 that the specific surface area of the crystal, the grain result and the aging property are improved after the alkaline earth metal is added.
4. It can be seen from examples 11 to 14 that, when alkaline earth metals are doped, the specific surface area of the crystal and the grain results show a tendency of increasing and then decreasing with increasing temperature, and the specific surface area in the aging property also shows a tendency of increasing and then decreasing, but the grain growth tendency in the aging property is that the grain growth rate gradually decreases with increasing temperature, wherein the aged properties of examples 8, 12 and 13 are significantly better than those of examples 11 and 14.
5. It can be seen from examples 15 to 17 that the amount of hydrogen peroxide has a certain effect on the properties of the crystals, but it has less effect than the precipitation temperature; specifically, when rare earth and alkaline earth metals are doped, the dosage of hydrogen peroxide is recommended to be controlled to be about 0.5-0.55 times.
6. As can be seen from comparative examples 3 to 5, the addition of ammonia water and the amount of rare earth elements can obviously affect the product performance.
The applicant states that the process of the invention is illustrated by the above examples, but the invention is not limited to the above process steps, which do not mean that the invention must be carried out in dependence on the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.

Claims (9)

1. The preparation method of the cerium-zirconium composite oxide is characterized by comprising the following steps:
step 1: adding hydrogen peroxide into an aqueous solution containing soluble cerium salt, soluble zirconium salt and soluble doped metal salt;
step 2: adding the solution obtained in the step 1 into a precipitator, controlling the pH of the solution to be 8-10, controlling the temperature to be 50-80 ℃ after the solution obtained in the step 1 is added, and stirring for 1-8 hours to enable metal ions in the soluble cerium salt, the soluble zirconium salt and the soluble doped metal salt to react with the precipitator to form metal salt precipitates;
step 3: separating the metal salt precipitate from the solution, washing and drying, and roasting at 700-900 ℃ for 3-5h;
the metal elements in the soluble doped metal salt comprise rare earth elements, wherein the rare earth elements are one or more of La, Y, pr, nd and Tb;
the mole ratio of cerium, zirconium and rare earth elements in the soluble cerium salt, the soluble zirconium salt and the soluble doped metal salt is 20-60: 30-70: 5 to 15.
2. The method for producing a cerium-zirconium composite oxide according to claim 1, wherein the temperature at the time of precipitation in the step 2 is 55 to 70 ℃.
3. The method for producing a cerium-zirconium composite oxide according to claim 1, wherein anions of the soluble cerium salt, the soluble zirconium salt, and the soluble doped metal salt are each independently chloride ion, nitrate ion, chloride ion, or sulfate ion.
4. The method according to claim 1, wherein in the step 1, the total concentration of metal ions in the soluble cerium salt, the soluble zirconium salt, and the soluble doped metal salt is 50 to 200mg/ml.
5. The method for producing a cerium-zirconium composite oxide according to claim 1, wherein the molar ratio of the addition amount of hydrogen peroxide to cerium element is 1:1 to 1:3.
6. The method for producing a cerium-zirconium composite oxide according to claim 5, wherein the molar ratio of the hydrogen peroxide to the cerium element is 1:1.8 to 1:2.
7. The method for producing a cerium-zirconium composite oxide according to claim 1, wherein the precipitant is one or more of aqueous ammonia, ammonium carbonate and ammonium bicarbonate; the precipitant is 1.2 times or more of the total equivalent of metal ions in the soluble cerium salt, the soluble zirconium salt and the soluble doped metal salt.
8. The method for producing a cerium-zirconium composite oxide according to any one of claims 1 to 7, wherein the metal element in the soluble doped metal salt comprises an alkaline earth metal element, and the alkaline earth metal element is one or more of Ca, sr, ba and Mg; the molar ratio of cerium, zirconium, rare earth elements and alkaline earth elements is 20-60: 30-70: 5-15: 0.1 to 5.
9. A cerium-zirconium composite oxide, characterized by being prepared by the method according to any one of claims 1 to 8.
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Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1193948A (en) * 1995-07-03 1998-09-23 罗纳·布朗克化学公司 Composition based on zirconium oxide and cerium oxide, preparation method therefor, and use thereof
CN1493519A (en) * 2002-10-29 2004-05-05 北京有色金属研究总院 Preparation of cerium zirconium composite oxide using coprecipitation-high pressure water heat combining method
US20130336864A1 (en) * 2012-06-15 2013-12-19 Basf Corporation Composites Of Mixed Metal Oxides For Oxygen Storage
CN103977782A (en) * 2013-02-07 2014-08-13 有研稀土新材料股份有限公司 Method using magnesium bicarbonate as precipitating agent for preparation of cerium zirconium class composite oxide
CN104525180A (en) * 2014-12-30 2015-04-22 长沙矿冶研究院有限责任公司 Preparation method for cerium-zirconium-aluminum-lanthanum-based oxygen storage material of mesoporous structure
CN105771955A (en) * 2016-04-14 2016-07-20 江门市科恒实业股份有限公司 Preparation method of ceria-zirconia solid solution
CN108349744A (en) * 2015-10-27 2018-07-31 镁电子有限公司 The composition based on zirconium oxide as three-way catalyst
CN110327909A (en) * 2019-06-11 2019-10-15 山东国瓷功能材料股份有限公司 A kind of preparation method of high oxygen storage capacity cerium zirconium compound oxide
CN111939894A (en) * 2020-09-17 2020-11-17 河北雄安稀土功能材料创新中心有限公司 Cerium-zirconium-based composite oxide with core-shell structure and preparation method thereof
CN113275000A (en) * 2021-07-23 2021-08-20 山东国瓷功能材料股份有限公司 High-temperature-resistant cerium-zirconium composite oxide and preparation method and application thereof
US20220184583A1 (en) * 2019-09-04 2022-06-16 Grirem Advanced Materials Co.,Ltd. Rare-earth-manganese/cerium-zirconium-based composite compound, method for preparing same and use thereof
US20220212172A1 (en) * 2019-08-09 2022-07-07 Shandong Sinocera Functional Materialco., Ltd Stable cerium-zirconium solid solution and preparation method therefor and application thereof

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1193948A (en) * 1995-07-03 1998-09-23 罗纳·布朗克化学公司 Composition based on zirconium oxide and cerium oxide, preparation method therefor, and use thereof
CN1493519A (en) * 2002-10-29 2004-05-05 北京有色金属研究总院 Preparation of cerium zirconium composite oxide using coprecipitation-high pressure water heat combining method
US20130336864A1 (en) * 2012-06-15 2013-12-19 Basf Corporation Composites Of Mixed Metal Oxides For Oxygen Storage
CN103977782A (en) * 2013-02-07 2014-08-13 有研稀土新材料股份有限公司 Method using magnesium bicarbonate as precipitating agent for preparation of cerium zirconium class composite oxide
CN104525180A (en) * 2014-12-30 2015-04-22 长沙矿冶研究院有限责任公司 Preparation method for cerium-zirconium-aluminum-lanthanum-based oxygen storage material of mesoporous structure
CN108349744A (en) * 2015-10-27 2018-07-31 镁电子有限公司 The composition based on zirconium oxide as three-way catalyst
CN105771955A (en) * 2016-04-14 2016-07-20 江门市科恒实业股份有限公司 Preparation method of ceria-zirconia solid solution
CN110327909A (en) * 2019-06-11 2019-10-15 山东国瓷功能材料股份有限公司 A kind of preparation method of high oxygen storage capacity cerium zirconium compound oxide
US20220212172A1 (en) * 2019-08-09 2022-07-07 Shandong Sinocera Functional Materialco., Ltd Stable cerium-zirconium solid solution and preparation method therefor and application thereof
US20220184583A1 (en) * 2019-09-04 2022-06-16 Grirem Advanced Materials Co.,Ltd. Rare-earth-manganese/cerium-zirconium-based composite compound, method for preparing same and use thereof
CN111939894A (en) * 2020-09-17 2020-11-17 河北雄安稀土功能材料创新中心有限公司 Cerium-zirconium-based composite oxide with core-shell structure and preparation method thereof
CN113275000A (en) * 2021-07-23 2021-08-20 山东国瓷功能材料股份有限公司 High-temperature-resistant cerium-zirconium composite oxide and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
岳梅等: "H2O2氧化对铈锆复合氧化物性能的影响研究", 稀有金属材料与工程, no. 12, 15 December 2014 (2014-12-15), pages 3109 - 3113 *
李维勇等: "液相沉淀法制备稀土-锆固溶体及其性能研究", 中国稀土学报, no. 02, 15 April 2010 (2010-04-15) *

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