CN1552517A - Preparation method of nano-scale cerium-zirconium rare earth composite oxide solid solution-based catalyst - Google Patents
Preparation method of nano-scale cerium-zirconium rare earth composite oxide solid solution-based catalyst Download PDFInfo
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- CN1552517A CN1552517A CNA2003101174534A CN200310117453A CN1552517A CN 1552517 A CN1552517 A CN 1552517A CN A2003101174534 A CNA2003101174534 A CN A2003101174534A CN 200310117453 A CN200310117453 A CN 200310117453A CN 1552517 A CN1552517 A CN 1552517A
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- 239000006104 solid solution Substances 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- -1 cerium-zirconium rare earth Chemical class 0.000 title claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 22
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 10
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 7
- MLHCSEGGTGAQHZ-UHFFFAOYSA-G [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zr+4].[Ce+3] Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zr+4].[Ce+3] MLHCSEGGTGAQHZ-UHFFFAOYSA-G 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 3
- 239000002244 precipitate Substances 0.000 claims abstract 4
- 239000000047 product Substances 0.000 claims abstract 4
- 239000012266 salt solution Substances 0.000 claims abstract 4
- 239000000126 substance Substances 0.000 claims abstract 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract 2
- 238000001035 drying Methods 0.000 claims description 16
- 238000001556 precipitation Methods 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 3
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 3
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000013078 crystal Substances 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 7
- 238000001914 filtration Methods 0.000 abstract description 6
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 238000009827 uniform distribution Methods 0.000 abstract 1
- 239000002002 slurry Substances 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000001354 calcination Methods 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 9
- QWDUNBOWGVRUCG-UHFFFAOYSA-N n-(4-chloro-2-nitrophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(Cl)C=C1[N+]([O-])=O QWDUNBOWGVRUCG-UHFFFAOYSA-N 0.000 description 9
- 150000002910 rare earth metals Chemical class 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000013049 sediment Substances 0.000 description 8
- 238000000352 supercritical drying Methods 0.000 description 7
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 6
- 241000370738 Chlorion Species 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000006210 lotion Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JRHFCLWPHIDLGN-UHFFFAOYSA-N cerium(3+) lanthanum(3+) oxygen(2-) praseodymium(3+) zirconium(4+) Chemical compound [O-2].[Zr+4].[Ce+3].[Pr+3].[La+3] JRHFCLWPHIDLGN-UHFFFAOYSA-N 0.000 description 2
- HLRPCWSWHIWFHM-UHFFFAOYSA-N cerium(3+) lanthanum(3+) oxygen(2-) zirconium(4+) Chemical class [O--].[O--].[O--].[O--].[O--].[Zr+4].[La+3].[Ce+3] HLRPCWSWHIWFHM-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000009938 salting Methods 0.000 description 2
- YDMWABAPBILCCW-UHFFFAOYSA-D [OH-].[Zr+4].[Ce+3].[La+3].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-] Chemical compound [OH-].[Zr+4].[Ce+3].[La+3].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-] YDMWABAPBILCCW-UHFFFAOYSA-D 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明涉及纳米级铈锆稀土复合氧化物固溶体基催化剂的制备方法。其包括如下步骤：1)将含铈的盐溶液和含锆的盐溶液按制品所含氧化铈及氧化锆的摩尔百分比混合；2)用碱性物质将混合物中和沉淀；3)过滤；4)用去离子水洗涤沉淀物，洗涤至洗液中用硝酸银检测无氯离子存在；5)洗涤后得到的铈锆氢氧化物并加水放入高压釜中进行水热反应；6)水热反应完毕后，将产物过滤，得到的沉淀物在同一高压釜中进行超临界干燥得纳米级铈锆复合氧化物固溶体催化剂。用本发明制备得到的纳米级铈锆稀土复合氧化物固溶体基催化剂的晶型为立方晶系，晶化程度高、晶体发育良好，粒径小且分布均匀、比表面积大、热稳定性好，其社会效益和经济效益均较显著。
The invention relates to a preparation method of a nano-scale cerium-zirconium rare earth composite oxide solid solution-based catalyst. It comprises the following steps: 1) mixing a cerium-containing salt solution and a zirconium-containing salt solution according to the mole percentage of cerium oxide and zirconium oxide contained in the product; 2) neutralizing and precipitating the mixture with an alkaline substance; 3) filtering; 4 ) washing the precipitate with deionized water, and washing until the presence of no chloride ions is detected with silver nitrate in the washing solution; 5) adding water to the cerium-zirconium hydroxide obtained after washing and putting it into an autoclave for hydrothermal reaction; 6) hydrothermal After the reaction is completed, the product is filtered, and the obtained precipitate is supercritically dried in the same autoclave to obtain a nanoscale cerium-zirconium composite oxide solid solution catalyst. The crystal form of the nano-scale cerium-zirconium rare earth composite oxide solid solution-based catalyst prepared by the present invention is a cubic crystal system, with high crystallization degree, good crystal development, small particle size and uniform distribution, large specific surface area, and good thermal stability. Its social and economic benefits are more significant.
Description
1, technical field:
The present invention relates to the catalyst based preparation method of nano-scale cerium zirconium complex rare-earth oxidate containing valuable metal solid solution, this type of catalyst is mainly used in the purifying vehicle exhaust catalyst aid, also can be used as other catalyst.
2, background technology:
Vehicle exhaust is one of main source of urban atmospheric pollution, is the important measures of guaranteeing environmental quality to the improvement of vehicle exhaust.At present, the measure of improvement is divided into emission controls by improving combustion and external purification.External purification mainly is to realize by the purifying vehicle exhaust catalytic unit, and the core of purifying vehicle exhaust catalytic unit is a catalyst.Nano-scale cerium zirconium complex rare-earth oxidate containing valuable metal solid solution is catalyst based to be a kind of catalyst aid of good purifying vehicle exhaust, because its adding, not only reduced the use amount of noble metal in the catalyst, and having improved catalytic activity, its oxygen storage capacity, mechanical strength and heat endurance all are improved.
Patent CN 1193948A discloses a kind of based on zirconia and cerium oxide composition, Preparation Method And The Use, 900 ℃ down the specific area of calcining after 6 hours be at least 30m
2/ g, and exist with the pure solid solution form of cerium oxide in zirconia.
Patent CN 1263868A discloses a kind of nanometer cerium zirconium oxide, and Preparation Method And The Use comprises the CeO of 4～98% (wt)
2ZrO with 1～95% (wt)
2, its composite oxides are to decompose and to obtain through preceding (the surpassing) that contain hydrazine or the hydrazonium salt thing that becomes under 200～1000 ℃.
Patent CN 1387943A discloses a kind of preparation technology based on cerium oxide and zirconia composite oxide solid solution, this composite oxide solid solution comprises cerium oxide 10～90% (wt), zirconia 10～90% (wt), it is characterized in that mixed reactant is behind alkali precipitation, sediment heat treatment, oven dry, calcining are made, be at least 35m in the specific area of calcining after 6 hours under 1000 ℃
2/ g, and exist with the pure solid solution form of cerium oxide in zirconia.
3, summary of the invention:
The objective of the invention is to overcome above-mentioned shortcoming and a kind of catalyst based method of Hydrothermal Preparation nano-scale cerium zirconium complex rare-earth oxidate containing valuable metal solid solution that adopts is provided.Calcine with catalyst based need not the passing through of nano-scale cerium zirconium complex rare-earth oxidate containing valuable metal solid solution that the present invention prepares, the crystal formation of the catalyst that obtains is a cubic system, crystallization degree height, crystal development are good, and particle diameter is little and be evenly distributed, specific area is big, Heat stability is good.
The present invention prepares the catalyst based method of nano-scale cerium zirconium complex rare-earth oxidate containing valuable metal solid solution, and it includes following steps:
1) salting liquid that will contain cerium mixes by goods institute's oxidation-containing cerium and zirconic molar percentage with the salting liquid that contains zirconium;
2) with alkaline matter with the mixture neutralization precipitation;
3) filter;
4) use deionized water washing sediment, wash to washing lotion and detect no chlorion existence with silver nitrate;
5) the cerium zirconium hydroxide that obtains and add water and put into autoclave and carry out hydro-thermal reaction after the washing;
6) after hydro-thermal reaction finishes, product is filtered, the sediment that obtains carries out supercritical drying and gets nano-scale cerium zirconium mixed oxide solid solution catalyst in same autoclave.
Above-mentioned steps 1) can add one or more rare earth element nitrate solution in.
Above-mentioned rare earth element nitrate can be obtained with nitric acid dissolve by lanthana, praseodymium oxide, neodymia, yittrium oxide.
Above-mentioned steps 1) except that the cerium zirconium, the molar percentage of the addition of other rare earth is 0～20% in.
Above-mentioned steps 2) adopt alkaline matter neutralization precipitation mixture, controlling its final pH value is 8.5～11.5.
Above-mentioned steps 2) alkaline matter that is adopted can be ammoniacal liquor, and the percentage by weight of its concentration is 10～28%, also can adopt the weak solution of NaOH.
Above-mentioned steps 2) precipitation temperature is 0～80 ℃.
Above-mentioned steps 5) hydrothermal reaction process control hydrothermal temperature is 140～300 ℃, and pressure is 0.6～4Mpa, and the time is 0.5～10h.
Above-mentioned steps 6) baking temperature is 100～300 ℃, and drying pressure is 7～10Mpa.
Above-mentioned steps 6) the nano-scale cerium zirconium mixed oxide solid solution catalyst of dry back gained comprises that the molar percentage of cerium oxide is 50～90%, zirconic molar percentage is 10～50%.
The present invention is owing to adopt Hydrothermal Preparation nano-scale cerium zirconium complex rare-earth oxidate containing valuable metal solid solution catalyst based, so the crystal formation of its product for preparing is a cubic system, crystallization degree height, crystal development are good, and particle diameter is little and be evenly distributed, specific area is big, Heat stability is good.Another characteristics of the present invention be after the hydro-thermal reaction in same reactor supercritical drying obtain product, need not to pass through again high-temperature calcination, thereby not only simplified operation, and the product specific area that makes is bigger, catalytic activity is better; Because reaction and drying are carried out at same reactor, have saved equipment investment, operating process is simpler, makes the powder granularity of gained controlled again, does not have reunion substantially.In addition, the present invention also is included in and can adds one or more other rare earth oxides in the cerium zirconium compound oxide solid solution, thereby further improves specific area, heat endurance, mechanical strength and the service life of catalyst, has improved its catalytic activity.The present invention not only technological process is simple, and the product quality height, and is free from environmental pollution.Catalyst based with the nano-scale cerium zirconium mixed oxide solid solution that the present invention makes, granularity is that specific area is greater than 100m between 5～20nm
2/ g, the proportioning of kind, quantity and the cerium zirconium of change additive can also make specific area up to 150～180m
2More than/the g, the specific area after 1000 ℃ calcining was worn out in 6 hours down is at least at 45m
2/ g.Should be noted that in the composite oxides of the present invention to have comprised hafnium, this is general and zirconium coexistence owing to hafnium in the mineral resources, and non-special reason does not need to separate in addition.The present invention is all significant catalyst based preparation method of nano-scale cerium zirconium complex rare-earth oxidate containing valuable metal solid solution of a kind of social benefit and economic benefit.
4, description of drawings:
Fig. 1 is the X-ray diffraction analysis chart with the product of the present invention's preparation;
Fig. 2 is the particle size distribution figure that records the product of embodiment 1 preparation with small-angle diffraction;
Fig. 3 is the particle size distribution figure that records the product of embodiment 2 preparations with small-angle diffraction;
Fig. 4 (a) is the TEM figure of the product of embodiment 3 preparations;
Fig. 4 (b) is the TEM figure of the product of embodiment 4 preparations.
5, the specific embodiment:
Embodiment 1:
Get cerous carbonate 30g, with the red fuming nitric acid (RFNA) dissolving, with mixing mutually after the basic zirconium chloride 25g dissolving, mix the back and come precipitation mixture with 25% (wt) ammoniacal liquor, control final pH=9.1, with the pure water washing, wash to washing lotion and detect no chlorion existence after precipitation is finished with silver nitrate.The cerium zirconium hydroxide that obtains after washing is good adds water, stirs into slurry with agitator, and slurry is put into autoclave carries out hydro-thermal reaction, 120 ℃ of control reaction temperatures, 8 hours time.After hydro-thermal reaction finishes, with the product cold filtration, the sediment that obtains is dissolved into slurry with ethanol, slurry is carried out supercritical drying in same autoclave, 2 hours drying times, the product that obtains after the drying is the nano cerium zirconium oxide, and the specific area of cerium Zirconium oxide after 1000 ℃ calcining was worn out in 6 hours down is 45m
2/ g.
X-ray diffraction the analysis showed that the oxide of acquisition exists with solid solution phase form, and x-ray diffraction pattern is seen a line among Fig. 1.
Small-angle diffraction records its particle size distribution and sees Fig. 2.
Embodiment 2:
Get cerous carbonate 20g, with the red fuming nitric acid (RFNA) dissolving, with mixing mutually after the basic zirconium chloride 15g dissolving, mix the back and come precipitation mixture with 25% (wt) ammoniacal liquor, control final pH=9.3, with the pure water washing, wash to washing lotion and detect no chlorion existence after precipitation is finished with silver nitrate.The cerium zirconium hydroxide that obtains after washing is good adds water, stirs into slurry with agitator, and slurry is put into autoclave carries out hydro-thermal reaction, 160 ℃ of control reaction temperatures, 5 hours time.After hydro-thermal reaction finishes, with the product cold filtration, the sediment that obtains is dissolved into slurry with ethanol, slurry is carried out supercritical drying in same autoclave, 4 hours drying times, the product that obtains after the drying is the nano cerium zirconium oxide, and the specific area of cerium Zirconium oxide after 1000 ℃ calcining was worn out in 6 hours down is 46m
2/ g.
X-ray diffraction the analysis showed that the oxide of acquisition exists with solid solution phase form, and x-ray diffraction pattern is seen the b line among Fig. 1.
Small-angle diffraction records its particle size distribution and sees Fig. 3.
Embodiment 3:
Get cerous carbonate 30g, lanthana 6g dissolves with red fuming nitric acid (RFNA) respectively, with mixing mutually after the basic zirconium chloride 25g dissolving, mix the back and come precipitation mixture with 25% (wt) ammoniacal liquor, control final pH=9.8, with the pure water washing, wash to washing lotion and detect no chlorion existence after precipitation is finished with silver nitrate.The cerium zirconium lanthanum hydroxide that obtains after washing is good adds water, stirs into slurry with agitator, and slurry is put into autoclave carries out hydro-thermal reaction, 180 ℃ of control reaction temperatures, 4.5 hours time.After hydro-thermal reaction finishes, with the product cold filtration, the sediment that obtains is dissolved into slurry with ethanol, slurry is carried out supercritical drying in same autoclave, 2 hours drying times, the product that obtains after the drying is the nano cerium zirconium lanthanum-oxides, and the specific area of cerium zirconium lanthanum-oxides after 1000 ℃ calcining was worn out in 6 hours down is 47m
2/ g.
X-ray diffraction the analysis showed that the oxide of acquisition exists with solid solution phase form, and finds that with the TEM detection product pellet of gained is evenly distributed, good dispersion, and its size is between 5～10 nanometers, and its TEM figure sees Fig. 4 (a).
Embodiment 4:
Get cerous carbonate 30g, lanthana 6g, praseodymium oxide 7g, dissolve with red fuming nitric acid (RFNA) respectively, with mixing mutually after the basic zirconium chloride 25g dissolving, mix the back and come precipitation mixture with 25% (wt) ammoniacal liquor, control final pH=10.5, with the pure water washing, wash to washing lotion and detect no chlorion existence after precipitation is finished with silver nitrate.The cerium zirconium lanthanum praseodymium hydroxide that obtains after washing is good adds water, stirs into slurry with agitator, and slurry is put into autoclave carries out hydro-thermal reaction, 250 ℃ of control reaction temperatures, 3 hours time.After hydro-thermal reaction finishes, with the product cold filtration, the sediment that obtains is dissolved into slurry with ethanol, slurry is carried out supercritical drying in same autoclave, 3 hours drying times, the product that obtains after the drying is a nano cerium zirconium lanthanum praseodymium oxide, and the specific area of cerium zirconium lanthanum praseodymium oxide after 1000 ℃ calcining was worn out in 6 hours down is 50m
2/ g.
X-ray diffraction the analysis showed that the oxide of acquisition exists with solid solution phase form, and finds that with the TEM detection product pellet of gained is evenly distributed, good dispersion, and its size is between 5～10 nanometers, and its TEM figure sees Fig. 4 (b).
Embodiment 5:
Get zirconium carbonate 30g, cerous carbonate 20g with the red fuming nitric acid (RFNA) dissolving, uses 25% (wt) ammoniacal liquor to precipitate again, controls final pH=10.5, washs with pure water after precipitation is finished.The cerium zirconium hydroxide that obtains after washing is good adds water, stirs into slurry with agitator, and slurry is put into autoclave carries out hydro-thermal reaction, 150 ℃ of control reaction temperatures, 6 hours time.After hydro-thermal reaction finishes, with the product cold filtration, the sediment that obtains is dissolved into slurry with ethanol, slurry is carried out supercritical drying in same autoclave, 2 hours drying times, the product that obtains after the drying is the nano cerium zirconium oxide, and the specific area of cerium Zirconium oxide after 1000 ℃ calcining was worn out in 6 hours down is 46m
2/ g.
X-ray diffraction the analysis showed that the oxide of acquisition exists with solid solution phase form, and x-ray diffraction pattern is seen c line among Fig. 1.
Embodiment 6:
Take by weighing a certain amount of basic zirconium chloride and cerous carbonate (is 1: 1 and 9: 1 two kinds of proportional arrangement presomas according to cerium oxide and zirconic molar percentage), step and method with reference to embodiment 1, the product that obtains after the drying is the nano cerium zirconium oxide, and the specific area of cerium Zirconium oxide after 1000 ℃ calcining was worn out in 6 hours down is respectively 49m
2/ g and 45m
2/ g.
Claims (10)
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100398448C (en) * | 2005-07-26 | 2008-07-02 | 中国科学院物理研究所 | Nano cerium oxide material with flower-like structure and its preparation method and application |
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| CN100445207C (en) * | 2005-07-22 | 2008-12-24 | 中国科学院物理研究所 | Nano-cerium oxide-based composite material with flower-like structure and its preparation method and application |
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| CN103249676A (en) * | 2010-11-30 | 2013-08-14 | 罗地亚管理公司 | Composition based on zirconium oxide and on at least one oxide of a rare earth other than cerium, having a specific porosity, processes for preparing same and use thereof in catalysis |
| CN103492068A (en) * | 2011-04-22 | 2014-01-01 | 三井金属矿业株式会社 | Carrier for internal-combustion engine exhaust gas purification catalyst |
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| CN107597113A (en) * | 2017-10-21 | 2018-01-19 | 福州大学 | A kind of preparation method and applications of the catalyst of cerium zirconium sosoloid containing ruthenium |
| US10106433B2 (en) | 2014-05-13 | 2018-10-23 | National Central University | Metal oxide nanoparticle material |
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| CN100445207C (en) * | 2005-07-22 | 2008-12-24 | 中国科学院物理研究所 | Nano-cerium oxide-based composite material with flower-like structure and its preparation method and application |
| CN100398448C (en) * | 2005-07-26 | 2008-07-02 | 中国科学院物理研究所 | Nano cerium oxide material with flower-like structure and its preparation method and application |
| CN100398199C (en) * | 2006-05-18 | 2008-07-02 | 浙江大学 | A kind of preparation method of high temperature resistant Ce-Zr composite alumina material |
| TWI469926B (en) * | 2008-12-04 | 2015-01-21 | Sakai Chemical Industry Co | Zirconium oxide dispersion, production thereof and resin composition containing the dispersion |
| CN103249676A (en) * | 2010-11-30 | 2013-08-14 | 罗地亚管理公司 | Composition based on zirconium oxide and on at least one oxide of a rare earth other than cerium, having a specific porosity, processes for preparing same and use thereof in catalysis |
| CN103249676B (en) * | 2010-11-30 | 2014-12-03 | 罗地亚管理公司 | Composition based on zirconium oxide and on at least one oxide of a rare earth other than cerium, having a specific porosity, processes for preparing same and use thereof in catalysis |
| CN103492068A (en) * | 2011-04-22 | 2014-01-01 | 三井金属矿业株式会社 | Carrier for internal-combustion engine exhaust gas purification catalyst |
| CN103492068B (en) * | 2011-04-22 | 2016-01-27 | 三井金属矿业株式会社 | For the carrier of purifying internal combustion engine tail gas catalyst |
| CN102513085A (en) * | 2011-11-07 | 2012-06-27 | 上海华明高纳稀土新材料有限公司 | Cerium oxide-zirconium oxide-based composite oxide and preparation method thereof |
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| US10106433B2 (en) | 2014-05-13 | 2018-10-23 | National Central University | Metal oxide nanoparticle material |
| CN107282032A (en) * | 2017-06-21 | 2017-10-24 | 广东科远高新材料有限责任公司 | A kind of zirconium oxide cerium oxide base rare earth compound solid solution oxide body and preparation method thereof |
| CN107597113A (en) * | 2017-10-21 | 2018-01-19 | 福州大学 | A kind of preparation method and applications of the catalyst of cerium zirconium sosoloid containing ruthenium |
| CN107597113B (en) * | 2017-10-21 | 2020-03-10 | 福州大学 | Preparation method and application of ruthenium-containing cerium-zirconium solid solution catalyst |
| CN110026176A (en) * | 2019-04-22 | 2019-07-19 | 山东国瓷功能材料股份有限公司 | A kind of cerium zirconium compound oxide, preparation method and application |
| CN110040760A (en) * | 2019-05-09 | 2019-07-23 | 常州大学 | A kind of method of controllable preparation cerium lanthanum-oxides solid solution nanometer rods |
| CN111135815A (en) * | 2019-12-26 | 2020-05-12 | 宣城晶瑞新材料有限公司 | Preparation method of high-purity nano cerium-zirconium solid solution material |
| CN111135815B (en) * | 2019-12-26 | 2023-04-07 | 宣城晶瑞新材料有限公司 | Preparation method of high-purity nano cerium-zirconium solid solution material |
| 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 |
| CN113275000B (en) * | 2021-07-23 | 2021-11-09 | 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 |
| CN115739173A (en) * | 2022-11-15 | 2023-03-07 | 昆明理工大学 | Denitration catalyst with stable structure, preparation method and application thereof, monolithic catalyst and application thereof |
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