CN102716733B - A kind of preparation method of high performance cerium zirconium aluminum oxygen-storage material - Google Patents
A kind of preparation method of high performance cerium zirconium aluminum oxygen-storage material Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of high performance cerium zirconium aluminum oxygen-storage material, comprise the following steps: 1) by diaspore: deionized water: the mass ratio of salpeter solution is 1: 10-20: 0.1-0.5 carry out mix and blend; 2) get the soluble-salt of zirconium and cerium and rare earth doping elements lanthanum, yttrium, Pu, Nd, add deionized water and make cerium zirconium mixed aqueous solution; 3) Alumina gel and cerium zirconium mixed liquor are pressed (Ce-Zr): Al
2o
3mass ratio is 1: 0.1-3 carry out mix and blend; 4) by the alkaline precipitating agent of organic polymer modifier and 2-6mol according to 5-10: 90-95 mass ratio mutually mix; 5) cerium zirconium aluminium complex sol and modified alkaline precipitating reagent are carried out mixing co-precipitation; 6) cerium zirconium aluminium hydroxide gel is carried out vacuum filtration and washing; 7) cerium zirconium aluminium hydroxide gel is placed in Muffle furnace calcines; 8) burned material is obtained cerium zirconium aluminium product through pulverizing.Preparation method's step of high performance cerium zirconium aluminum oxygen-storage material of the present invention is simple, and obtained cerium zirconium aluminium hydrogen-storing material has good high thermal stability.
Description
Technical field
The present invention relates to a kind of preparation method of high performance cerium zirconium aluminum oxygen-storage material.
Background technology
Cerium zirconium aluminum composite oxides is a kind of novel rare earth oxygen storage material, has the Common advantages of hydrogen-storing material and activated alumina concurrently.Thus it shows more excellent heat endurance and oxygen storage capacity in three-effect catalysis purification (TWC), catalytic combustion, diesel engine DOC, POC purification.
The method preparing cerium zirconium aluminum composite oxides at present mainly contains infusion process, coprecipitation, sol-gel process, microemulsion method, mechanical mixing etc.Wherein, coprecipitation is widely used because technique is simple, condition is easy to control, product homogeneity is good, production cost is lower, be convenient to the advantages such as suitability for industrialized production, but existing coprecipitation step is complicated, and production cost is high.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of preparation method of high performance cerium zirconium aluminum oxygen-storage material, step is simple, and obtained cerium zirconium aluminium hydrogen-storing material has excellent heat endurance and oxygen storage capacity.
The preparation method of high-performance cerium chromium aluminium hydrogen-storing material of the present invention, comprises the following steps:
1) boehmite nitric acid reaction is made Alumina gel, diaspore: deionized water: the mass ratio of salpeter solution is 1: 10-20: 0.1-0.5 carry out mix and blend, obtains finely dispersed Alumina gel, Al in diaspore
2o
3mass fraction be 70%, in salpeter solution, the mass fraction of nitric acid is 60%;
2) get the soluble-salt of zirconium and cerium and rare earth doping elements lanthanum, yttrium, Pu, Nd, add deionized water and make the cerium zirconium mixed aqueous solution that total ion concentration is 0.5-1.5mol/l, in described mixed liquor, the mol ratio of Ce and Zr is 1: 0.5-3; Rare earth doping elements is one or more in lanthanum, yttrium, Pu, Nd, and weight accounts for the 2-10% of cerium zirconium;
3) by step 1) Alumina gel that obtains and step 2) the cerium zirconium mixed liquor that obtains is by (Ce-Zr): Al
2o
3mass ratio is 1: 0.1-3 carry out mix and blend, obtains finely dispersed cerium zirconium aluminium complex sol, and to control its oxide total concentration be 50-100g/l;
4) by the alkaline precipitating agent of organic polymer modifier and 2-6mol according to 5-10: 90-95 mass ratio mutually mix, obtain modified alkaline precipitating reagent;
5) by step 3) the cerium zirconium aluminium complex sol that obtains and step 4) the modified alkaline precipitating reagent that obtains carries out mixing co-precipitation, and control terminal PH > 8, obtain cerium zirconium aluminium hydroxide gel;
6) cerium zirconium aluminium hydroxide gel is carried out vacuum filtration and washing, control washing electrical conductivity < 20ms/cm;
7) by step 6) the cerium zirconium aluminium hydroxide gel that obtains is placed in calcining in Muffle furnace, control temperature 700-800 DEG C, calcining 2-6 hour;
8) by step 7) burned material that obtains obtains the cerium zirconium aluminium product of different-grain diameter through mechanical crushing or air-flow crushing.
The preparation method of high performance cerium zirconium aluminum oxygen-storage material of the present invention, in step 2) in: the soluble-salt of described cerium is cerous nitrate, ammonium ceric nitrate, cerous acetate, cerium chloride, the soluble-salt of described zirconium is zirconium nitrate, acetic acid zirconium, zirconium oxychloride, and the soluble-salt of described rare earth doping elements lanthanum, yttrium, Pu, Nd is nitrate, acetate, chloride.
The preparation method of high performance cerium zirconium aluminum oxygen-storage material of the present invention, in step 4) in: described organic polymer modifier organic polymer acids or alcohols.
The preparation method of high performance cerium zirconium aluminum oxygen-storage material of the present invention, in step 4) in: described alkaline precipitating agent is one or more in ammoniacal liquor, ammonium carbonate, carbonic hydroammonium.
Compared with prior art beneficial effect of the present invention is: preparation method's step of high performance cerium zirconium aluminum oxygen-storage material of the present invention is simple, with the zirconates of boehmite, solubility and cerium salt for raw material, carry out peptization reaction and make colloidal sol, take alkali as precipitating reagent, organic polymer acids, alcohols are modifier, by colloidal sol through organically-modified alkali lye precipitation after, sediment filtered, washs, calcine, pulverize obtained.Obtained cerium zirconium aluminium hydrogen-storing material calcination 2-6 hour under the condition of 700 DEG C-800 DEG C, tests its fresh specific area 120-140m
2/ g, the hours aging specific area > 60m of calcination 10 under the condition of 1000 DEG C
2/ g, the hours aging specific area > 40m of calcination 10 under the condition of 1100 DEG C
2/ g, obtained cerium zirconium aluminium hydrogen-storing material has good high thermal stability.
Detailed description of the invention
Below in conjunction with embodiment, the specific embodiment of the present invention is described in further detail.Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
Get 64.3g boehmite (Al
2o
3: 70%), add deionized water 800ml, salpeter solution (nitric acid mass fraction is 60%) 12ml mix and blend obtains Alumina gel; Get cerous nitrate 66.7ml (TREO:225g/L), zirconium nitrate 148.5ml (ZrO respectively
2: 202g/L), after lanthanum nitrate 20.8ml (TREO:240g/L), yttrium nitrate 20.8ml (TREO:240g/L) mixing, join in Alumina gel, and add pure water and be diluted to 1500ml, obtaining mass ratio is CeO
2: ZrO
2: La
2o
3: Y
2o
3: Al
2o
3the cerium zirconium Alumina gel of=15: 30: 5: 5: 45; Modified aluminium colloidal sol is at room temperature joined in the ammoniacal liquor of the 4.6mol/L being dissolved with 7.6% polymeric organic acid and precipitate, controlling final PH is 8.3, after precipitation, vacuum filtration and washing are 18ms/cm to the electrical conductivity in washing lotion, obtain cerium zirconium aluminium hydroxide gel.Cerium zirconium alumina gel is obtained cerium zirconium aluminum oxide for 4 hours 700 DEG C of calcinings, and testing its specific area is 132.6m
2/ g, 1000 DEG C of 10 hours aging specific area is 66.8m
2/ g, 1100 DEG C of 10 hours aging specific area is 45.5m
2/ g.
Embodiment 2
Get 64.3g boehmite (Al
2o
3: 70%), add deionized water 800ml, salpeter solution (nitric acid mass fraction is 60%) 15ml mix and blend obtains Alumina gel; Get cerous nitrate 133.3ml (TREO:225g/L), zirconium nitrate 74.2ml (ZrO respectively
2: 202g/L), after lanthanum nitrate 20.8ml (TREO:240g/L), yttrium nitrate 20.8ml (TREO:240g/L) mixing, join in Alumina gel, and add pure water and be diluted to 1500ml, obtaining mass ratio is CeO
2: ZrO
2: La
2o
3: Y
2o
3: Al
2o
3the cerium zirconium Alumina gel of=30: 15: 5: 5: 45; Modified aluminium colloidal sol is at room temperature joined in the ammoniacal liquor of the 3.2mol/L being dissolved with 6.5% polymeric organic acid and precipitate, controlling final PH is 8.5, after precipitation, vacuum filtration and washing are 16ms/cm to the electrical conductivity in washing lotion, obtain cerium zirconium aluminium hydroxide gel.Calcined under the condition of 700 DEG C by cerium zirconium alumina gel and obtain cerium zirconium aluminum oxide in 4 hours, testing its specific area is 126.3m
2/ g, calcining 10 hours aging specific areas under the condition of 1000 DEG C is 62.6m
2/ g, calcining 10 hours aging specific areas under the condition of 1100 DEG C is 42.7m
2/ g.
Embodiment 3
Get 42.8g boehmite (Al
2o
3: 70%), add deionized water 600ml, salpeter solution (nitric acid mass fraction is 60%) 10ml mix and blend obtains Alumina gel; After getting cerous nitrate 133.3ml (TREO:225g/L), zirconium nitrate 148.5ml (ZrO2:202g/L), lanthanum nitrate 20.8ml (TREO:240g/L), yttrium nitrate 20.8ml (TREO:240g/L) mixing respectively, join in Alumina gel, and add pure water and be diluted to 1500ml, obtaining mass ratio is CeO
2: ZrO
2: La
2o
3: Y
2o
3: Al
2o
3the cerium zirconium Alumina gel of=30: 30: 5: 5: 30; At room temperature joined by modified aluminium colloidal sol in the ammoniacal liquor of the 4mol/L being dissolved with 8% polymeric organic acid and precipitate, controlling final PH is 9.2, and after precipitation, vacuum filtration and washing are 12ms/cm to the electrical conductivity in washing lotion, obtain cerium zirconium aluminium hydroxide gel.Cerium zirconium alumina gel is obtained cerium zirconium aluminum oxide for 4 hours 700 DEG C of calcinings, and testing its specific area is 125m2/g, and calcining 10 hours aging specific areas under the condition of 1000 DEG C is 63m
2/ g, calcining 10 hours aging specific areas under the condition of 1100 DEG C is 41m
2/ g.
Preparation method's step of high performance cerium zirconium aluminum oxygen-storage material of the present invention is simple, with the zirconates of boehmite, solubility and cerium salt for raw material, carry out peptization reaction and make colloidal sol, take alkali as precipitating reagent, organic polymer acids, alcohols are modifier, by colloidal sol through organically-modified alkali lye precipitation after, sediment filtered, washs, calcine, pulverize obtained.Obtained cerium zirconium aluminium hydrogen-storing material calcination 2-6 hour under the condition of 700 DEG C-800 DEG C, testing its fresh specific area is 120-140m
2/ g, the hours aging specific area > 60m of calcination 10 under the condition of 1000 DEG C
2/ g, the hours aging specific area > 40m of calcination 10 under the condition of 1100 DEG C
2/ g, obtained cerium zirconium aluminium hydrogen-storing material has good high thermal stability.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvement and modification, these improve and modification also should be considered as protection scope of the present invention.
Claims (3)
1. a preparation method for high performance cerium zirconium aluminum oxygen-storage material, is characterized in that, comprises the following steps:
1) boehmite nitric acid reaction is made Alumina gel, diaspore: deionized water: the mass ratio of salpeter solution is 1: 10-20: 0.1-0.5 carry out mix and blend, obtains finely dispersed Alumina gel, Al in diaspore
2o
3mass fraction be 70%, in salpeter solution, the mass fraction of nitric acid is 60%;
2) get the soluble-salt of zirconium and cerium and rare earth doping elements lanthanum, yttrium, Pu, Nd, add deionized water and make the cerium zirconium mixed aqueous solution that total ion concentration is 0.5-1.5mol/l, in described mixed liquor, the mol ratio of Ce and Zr is 1: 0.5-3; Rare earth doping elements is one or more in lanthanum, yttrium, Pu, Nd, and weight accounts for the 2-10% of cerium zirconium;
3) by step 1) Alumina gel that obtains and step 2) the cerium zirconium mixed liquor that obtains is by (Ce-Zr): Al
2o
3mass ratio is 1: 0.1-3 carry out mix and blend, obtains finely dispersed cerium zirconium aluminium complex sol, and to control its oxide total concentration be 50-100g/L;
4) by the alkaline precipitating agent of organic polymer modifier and 2-6mol according to 5-10: 90-95 mass ratio mutually mix, obtain modified alkaline precipitating reagent; Described organic polymer modifier organic polymer acids or alcohols;
5) by step 3) the cerium zirconium aluminium complex sol that obtains and step 4) the modified alkaline precipitating reagent that obtains carries out mixing co-precipitation, and control terminal PH > 8, obtain cerium zirconium aluminium hydroxide gel;
6) cerium zirconium aluminium hydroxide gel is carried out vacuum filtration and washing, control washing electrical conductivity < 20ms/cm;
7) by step 6) the cerium zirconium aluminium hydroxide gel that obtains is placed in calcining in Muffle furnace, control temperature 700-800 DEG C, calcining 2-6 hour;
8) by step 7) burned material that obtains obtains the cerium zirconium aluminium product of different-grain diameter through mechanical crushing or air-flow crushing.
2. the preparation method of high performance cerium zirconium aluminum oxygen-storage material according to claim 1, it is characterized in that, in step 2) in: the soluble-salt of described cerium is cerous nitrate, ammonium ceric nitrate, cerous acetate, cerium chloride, the soluble-salt of described zirconium is zirconium nitrate, acetic acid zirconium, zirconium oxychloride, and the soluble-salt of described rare earth doping elements lanthanum, yttrium, Pu, Nd is nitrate, acetate, chloride.
3. the preparation method of high performance cerium zirconium aluminum oxygen-storage material according to claim 1, is characterized in that, in step 4) in: described alkaline precipitating agent is one or more in ammoniacal liquor, ammonium carbonate, carbonic hydroammonium.
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| CN104128173B (en) * | 2014-08-12 | 2016-05-18 | 淄博加华新材料资源有限公司 | Low-cost and high-performance carried catalyst and preparation method thereof |
| CN104190438B (en) * | 2014-08-12 | 2017-02-01 | 淄博加华新材料资源有限公司 | High-performance cerium zirconium oxide and production method of high-performance cerium zirconium oxide |
| CN107349923B (en) * | 2017-07-10 | 2020-07-21 | 中自环保科技股份有限公司 | Mixed component material and preparation method thereof |
| CN107694556A (en) * | 2017-10-17 | 2018-02-16 | 高俊 | A kind of preparation method of high storage oxygen high heat stability type hydrogen-storing material |
| CN108970602B (en) * | 2018-08-01 | 2021-05-28 | 湖南稀土金属材料研究院 | Oxygen storage material and preparation method and application thereof |
| US20230398532A1 (en) * | 2020-10-29 | 2023-12-14 | Basf Corporation | Three-way diesel catalyst for cold start technology |
| EP4269351A4 (en) * | 2020-12-24 | 2024-06-26 | Mitsui Mining & Smelting Co., Ltd. | Composite oxide and method for producing same |
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