CN103127925A - Cerium-zirconium-based solid solution rare earth oxygen-storage material and preparation method thereof - Google Patents
Cerium-zirconium-based solid solution rare earth oxygen-storage material and preparation method thereof Download PDFInfo
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- CN103127925A CN103127925A CN2011103776171A CN201110377617A CN103127925A CN 103127925 A CN103127925 A CN 103127925A CN 2011103776171 A CN2011103776171 A CN 2011103776171A CN 201110377617 A CN201110377617 A CN 201110377617A CN 103127925 A CN103127925 A CN 103127925A
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 71
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 71
- 239000006104 solid solution Substances 0.000 title claims abstract description 61
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000011232 storage material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 150000007524 organic acids Chemical class 0.000 claims abstract description 11
- 239000012266 salt solution Substances 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000004381 surface treatment Methods 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 59
- 239000001301 oxygen Substances 0.000 claims description 59
- 229910052760 oxygen Inorganic materials 0.000 claims description 59
- 239000000243 solution Substances 0.000 claims description 25
- 229910002651 NO3 Inorganic materials 0.000 claims description 21
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 21
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 20
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 20
- 239000003153 chemical reaction reagent Substances 0.000 claims description 18
- 230000001376 precipitating effect Effects 0.000 claims description 18
- 229910052684 Cerium Inorganic materials 0.000 claims description 15
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 230000018044 dehydration Effects 0.000 claims description 11
- 238000006297 dehydration reaction Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 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
- -1 yittrium oxide Chemical compound 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 230000003750 conditioning effect Effects 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical group CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- 229940070765 laurate Drugs 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-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 4
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- 229940014800 succinic anhydride Drugs 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 9
- 238000001556 precipitation Methods 0.000 abstract description 7
- 230000032683 aging Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 2
- 239000008187 granular material Substances 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000007084 catalytic combustion reaction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
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- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- FZMFJORHWIAQFU-UHFFFAOYSA-N [Y].[Zr].[Ce] Chemical compound [Y].[Zr].[Ce] FZMFJORHWIAQFU-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
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- 229910052758 niobium Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
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- 229910052727 yttrium Inorganic materials 0.000 description 1
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Abstract
The invention discloses a cerium-zirconium-based solid solution rare earth oxygen-storage material and a preparation method thereof. The cerium-zirconium-based solid solution rare earth oxygen-storage material has a specific surface area equal to or greater than 90m<2>.g<-1>, has a specific surface area equal to or greater than 30m<2>.g<-1> after being calcined at a temperature of 1000 DEG C for 4 hours, and has a specific surface area equal to or greater than 20m<2>.g<-1> after being calcined at a temperature of 1050 DEG C for 12 hours. Compared with the prior art, the preparation method has the advantages that before precipitation, a mixed metal salt solution is added with a certain amount of an organic acid so that acidity of the mixed metal salt solution is improved or the mixed metal salt solution forms sol; a reaction rate is inhibited and a precipitation rate is controlled so that a stable precursor having the uniform grain size is obtained; and the precipitate precursor surface treatment is carried out by a surfactant so that the aperture size and the aperture volume of a calcination product are improved and the cerium-zirconium-based solid solution rare earth oxygen-storage material having good heat stability is prepared. The cerium-zirconium-based solid solution rare earth oxygen-storage material has the advantages of small granule size, large specific surface area, high temperature aging resistance and high activity.
Description
Technical field
The present invention relates to a kind of rare earth oxygen storage material and preparation method thereof, particularly a kind ofly eliminate and the cerium zirconium based solid solution rare earth oxygen storage material of the waste gas purification such as natural gas catalytic combustion or catalytic combustion and preparation method thereof for purifying vehicle exhaust, organic exhaust gas.
Background technology
Reducing automobile exhaust pollution, environment protection quality, realize the sustainable development of ecological environment and society, is one of important topic that reaches at present China environmental protection in the following long duration.
In order to reduce pollution, must break through from improving gasoline quality, improve the engine combustion state and increasing exhaust purification catalytic efficient three aspects:.Up to the present, that effective way is exactly to reduce the content of HC in tail gas, CO and three kinds of toxic gases of NOx by three-way catalytic apparatus with cleaning catalyst for tail gases of automobiles, and hydrogen-storing material is the important component part in the three-element catalytic reforming unit, it plays the effect of regulating atmosphere in the tail gas clean-up process, when atmosphere is in lean burn condition, hydrogen-storing material will absorb unnecessary oxygen, when atmosphere is in fuel-rich state, hydrogen-storing material is emitted oxygen, and three kinds of gases are effectively transformed.Therefore, the quality of the storage oxygen performance of hydrogen-storing material directly affects the transformation efficiency of tail gas.The effectively dispersion of stabilizing active component of hydrogen-storing material simultaneously, therefore have large specific area, larger pore volume and suitable pore-size distribution, and the cerium zirconium based oxygen storage material with good high-temperature aging resisting performance, excellent low-temperature catalyzed performance becomes the critical material of new three-way catalyst.
ZrO
2Add CeO to
2In, can form CeO
2-ZrO
2Solid solution and improve CeO
2The body phase behaviour, be beneficial to migration and the diffusion of body phase oxygen atom, body phase reaction process is become vivaciously, can improve CeO
2Oxygen storage capacity and high-temperature stability.Simultaneously, the rare earth such as Pr, Nd, Y, Nb, La and Ba and alkaline earth element add the high-temperature aging resisting that can further strengthen hydrogen-storing material, improve its oxygen storage capacity.
The Chinese patent patent No. is that the patent of invention of ZL200510115874.2 discloses a kind of solid solution composition of cerium zirconium compound oxide with high specific surface and preparation method thereof, add surfactant or amine salt or inorganic ammonium salt or ethanol in the suspension that is settled out by being added on, and high temperature crystallization, after crystallization, product washs through ethanol, high-temperature roasting.
But, above-mentioned complicated process of preparation, simultaneously by the high temperature crystallization, the ethanol washing is unfavorable for industrial production, and is common liquid-phase precipitation during precipitation, particle is larger.
China Patent Publication No. is that the patent of invention of CN101637721B discloses a kind of porous yttrium-cerium-zirconium solid solution and preparation method thereof; by adding protective agent, norium salting liquid and active polystyrene microballoon emulsion; the normal temperature precipitation; 80-100 ℃ of ageing, collecting precipitation thing, washing, drying, roasting get target product.
In above-mentioned preparation method, polystyrene microsphere emulsion and metal salt solution can't mix, and easily cause the stable homogeneous of product.
China Patent Publication No. is that the patent of invention of CN100496745C discloses a kind of wire or rod-like polycrystal Ce
0.6Zr
0.3Y
0.1O
2The solid solution preparation method by adding softex kw as surfactant, gets presoma by hydrothermal treatment consists, and calcination gets target product.
Above-mentioned preparation method needs high-tension apparatus by hydrothermal treatment consists, is unfavorable for industrialization production.
Therefore, need especially a kind of cerium zirconium based solid solution rare earth oxygen storage material and preparation method thereof, solved the problem of above-mentioned existing existence.
Summary of the invention
The object of the present invention is to provide a kind of cerium zirconium based solid solution rare earth oxygen storage material and preparation method thereof, overcome prior art and have above-mentioned problem, the cerium zirconium based solid solution rare earth oxygen storage material of preparation, have that particle is little, specific area is large, high-temperature aging resisting and active high, satisfies business to production cost and the requirement to environmental limitations that day by day increases.
To achieve these goals, technical scheme of the present invention is as follows:
A first aspect of the present invention provides a kind of cerium zirconium based solid solution rare earth oxygen storage material, it is characterized in that its specific surface 〉=90m
2G
-1, specific surface 〉=30m after 1000 ℃ of roasting 4h
2G
-1, specific surface 〉=20m after 1050 ℃ of roasting 12h
2G
-1
A second aspect of the present invention provides a kind of preparation method of cerium zirconium based solid solution rare earth oxygen storage material, it is characterized in that, it comprises the steps:
(1) preparation of hybrid metal nitrate solution: according to the weight of material component formation and target product, determine the content of cerium oxide, zirconia and other rare earth oxides except cerium, be converted into the weight content of corresponding raw material, cerous nitrate, other rare earth solubility nitrate and zirconium nitrate except cerium is water-soluble, add certain organic acid, get the hybrid metal nitrate solution;
(2) preparation of cerium zirconium based solid solution rare earth oxygen storage material presoma: 1: 1 mixed precipitating reagent of the industrial ammonia with 36% and pure water, slowly join in the hybrid metal nitrate solution of 50-70 ℃, to pH be 3-4, add Ce
3+/ Ce
4+Transform the stoichiometry 1.2-1.5 hydrogen peroxide doubly that needs, continuing to add precipitating reagent is 9 to pH, insulation 2-5h, and washing, dehydration get cerium zirconium based solid solution rare earth oxygen storage material presoma;
(3) surface treatment of cerium zirconium based solid solution rare earth oxygen storage material presoma: cerium zirconium based solid solution rare earth oxygen storage material presoma and certain surfactant are sheared disperseed;
(4) roasting: surface treated cerium zirconium based solid solution rare earth oxygen storage material presoma at 450-800 ℃ of lower roasting 4-8h, is got described cerium zirconium based solid solution rare earth oxygen storage material.
In one embodiment of the invention, described other rare earth solubility nitrate except cerium are selected from one or more the combination in lanthanum nitrate, yttrium nitrate, praseodymium nitrate or neodymium nitrate.
In one embodiment of the invention, described other rare earth solubility nitrate except cerium are selected from nitric acid and lanthana, yittrium oxide, praseodymium oxide or the corresponding nitrate solution of neodymia reaction generation.
In one embodiment of the invention, in described hybrid metal nitrate solution, the ratio of each nitrate is:
Cerous nitrate 20-70%
Zirconium nitrate 20-70%
Other rare earth solubility nitrate 5-15% except cerium.
In one embodiment of the invention, described organic acid is one or more combination in acetic acid, formic acid or citric acid, and described organic acid addition accounts for the 5-20% of nitrate weight in mixed salt solution by weight.
In one embodiment of the invention, described surface conditioning agent is selected from laurate, stearic acid or alkenyl succinic anhydride the combination of one or more, and the addition of described surface conditioning agent is counted 30-50% with the weight of described cerium zirconium based solid solution rare earth oxygen storage material.
Cerium zirconium based solid solution rare earth oxygen storage material of the present invention and preparation method thereof, compare with existing product, add certain organic acid in mixed salt solution before precipitation, improve the acidity of mixed salt solution or form colloidal sol, the speed of inhibitory reaction, control settling velocity, to obtaining uniform particle diameter, stable presoma; And carry out surface treatment by surfactant at the sediment presoma, improve aperture, the pore volume of product of roasting, obtain the cerium zirconium based solid solution rare earth oxygen storage material of good thermal stability, it is little that the cerium zirconium based solid solution rare earth oxygen storage material for preparing has a particle, specific area is large, high temperature ageing resistance and active advantages of higher, realizes purpose of the present invention.
Characteristics of the present invention can be consulted the detailed description of the graphic and following better embodiment of this case and be obtained to be well understood to.
Description of drawings
Fig. 1 is the schematic diagram that the XRD of the cerium zirconium based solid solution rare earth oxygen storage material of embodiments of the invention 1 contrasts.
The specific embodiment
For technological means, creation characteristic that the present invention is realized, reach purpose and effect is easy to understand, further set forth the present invention below in conjunction with specific embodiment.
Cerium zirconium based solid solution rare earth oxygen storage material of the present invention, its specific surface 〉=90m
2G
-1, specific surface 〉=30m after 1000 ℃ of roasting 4h
2G
-1, specific surface 〉=20m after 1050 ℃ of roasting 12h
2G
-1
The preparation method of cerium zirconium based solid solution rare earth oxygen storage material of the present invention, it comprises the steps:
(1) preparation of hybrid metal nitrate solution: according to the weight of material component formation and target product, determine the content of cerium oxide, zirconia and other rare earth oxides except cerium, be converted into the weight content of corresponding raw material, cerous nitrate, other rare earth solubility nitrate and zirconium nitrate except cerium is water-soluble, add certain organic acid, get the hybrid metal nitrate solution;
(2) preparation of cerium zirconium based solid solution rare earth oxygen storage material presoma: 1: 1 mixed precipitating reagent of the industrial ammonia with 36% and pure water, slowly join in the hybrid metal nitrate solution of 50-70 ℃, to pH be 3-4, add Ce
3+/ Ce
4+Transform the stoichiometry 1.2-1.5 hydrogen peroxide doubly that needs, continuing to add precipitating reagent is 9 to pH, insulation 2-5h, and washing, dehydration get cerium zirconium based solid solution rare earth oxygen storage material presoma;
(3) surface treatment of cerium zirconium based solid solution rare earth oxygen storage material presoma: cerium zirconium based solid solution rare earth oxygen storage material presoma and certain surfactant are sheared disperseed;
(4) roasting: surface treated cerium zirconium based solid solution rare earth oxygen storage material presoma at 450-800 ℃ of lower roasting 4-8h, is got described cerium zirconium based solid solution rare earth oxygen storage material.
In above-mentioned steps (1), described other rare earth solubility nitrate except cerium are selected from one or more the combination in lanthanum nitrate, yttrium nitrate, praseodymium nitrate or neodymium nitrate; Described other rare earth solubility nitrate except cerium are selected from nitric acid and lanthana, yittrium oxide, praseodymium oxide or neodymia reaction generate corresponding nitrate solution.
In described hybrid metal nitrate solution, the ratio of each nitrate is:
Cerous nitrate 20-70%
Zirconium nitrate 20-70%
Other rare earth solubility nitrate 5-15% except cerium.
Described organic acid is one or more combination in acetic acid, formic acid or citric acid, and described organic acid addition accounts for the 5-20% of nitrate weight in mixed salt solution by weight.
In above-mentioned steps (3), described surface conditioning agent is selected from laurate, stearic acid or alkenyl succinic anhydride the combination of one or more, and the addition of described surface conditioning agent is counted 30-50% with the weight of described cerium zirconium based solid solution rare earth oxygen storage material.
Embodiment 1
The 70g cerous nitrate, the 20g zirconium nitrate, the 5g lanthanum nitrate, the 5g yttrium nitrate is dissolved in the 1900g deionized water, adds 5g acetic acid, is heated to 50 ℃, gets the hybrid metal nitrate solution; Industrial ammonia is mixed with mass ratio with pure water at 1: 1, gets precipitating reagent, precipitating reagent is slowly added to get the hybrid metal nitrate solution, to the pH value be 3, after adding the 11.6g hydrogen peroxide, continuing to add precipitating reagent to pH value is 9, the insulation 5h; Washing, dehydration; Cerium zirconium based solid solution rare earth oxygen storage material presoma after dehydration is mixed with the 11g laurate, shear and disperse, 600 ℃ of lower roasting 4h get described cerium zirconium based solid solution rare earth oxygen storage material.
The specific surface of described cerium zirconium based solid solution rare earth oxygen storage material is 100.55m
2G
-1, particle size is 90nm, the XRD schematic diagram is referring to Fig. 1.Getting cerium zirconium based solid solution rare earth oxygen storage material specific surface after 1000 ℃ of roasting 4h is 45.32m
2G
-1, after 1050 ℃ of roasting 12h, specific surface is 25.32m
2G
-1
Embodiment 2
The 21g cerous nitrate, the 133g zirconium nitrate, the 5.5g neodymium nitrate, the 1.5g yttrium nitrate is dissolved in the 1900g deionized water, adds the 32g citric acid, is heated to 70 ℃, gets the hybrid metal nitrate solution; Industrial ammonia is mixed with mass ratio with pure water at 1: 1, gets precipitating reagent, precipitating reagent is slowly added to get the hybrid metal nitrate solution, to the pH value be 3, after adding the 4.4g hydrogen peroxide, continuing to add precipitating reagent to pH value is 9, the insulation 2h; Washing, dehydration; With cerium zirconium based solid solution rare earth oxygen storage material presoma and the 30g alkenyl succinic anhydride after dehydration, shear and disperse, 450 ℃ of lower roasting 8h get described cerium zirconium based solid solution rare earth oxygen storage material.
The specific surface of described cerium zirconium based solid solution rare earth oxygen storage material is 120.18m
2G
-1, getting cerium zirconium based solid solution rare earth oxygen storage material specific surface after 1000 ℃ of roasting 4h is 35.86m
2G
-1, after 1050 ℃ of roasting 12h, specific surface is 27.38m
2G
-1
Embodiment 3
With the 5g lanthana, 5g yittrium oxide nitric acid dissolve adds the 100g cerous nitrate after getting clear solution, and the 72g zirconium nitrate adds deionized water to 2000g, adds 20g formic acid, is heated to 70 ℃; Get the hybrid metal nitrate solution; Industrial ammonia is mixed with mass ratio with pure water at 1: 1, gets precipitating reagent, precipitating reagent is slowly added to get the hybrid metal nitrate solution, to the pH value be 3, after adding the 20g hydrogen peroxide, continuing to add precipitating reagent to pH value is 9, the insulation 4h; Washing, dehydration; With cerium zirconium based solid solution rare earth oxygen storage material presoma and the 30g stearic acid after dehydration, shear and disperse, 800 ℃ of lower roasting 4h get described cerium zirconium based solid solution rare earth oxygen storage material.
The specific surface of described cerium zirconium based solid solution rare earth oxygen storage material is 100.02m
2G
-1, getting cerium zirconium based solid solution rare earth oxygen storage material specific surface after 1000 ℃ of roasting 4h is 31.28m
2G
-1, after 1050 ℃ of roasting 12h, specific surface is 23.12m
2G
-1
Embodiment 4
With the 7g praseodymium oxide, 7g neodymia nitric acid dissolve adds the 76g cerous nitrate after getting clear solution, and the 145g zirconium nitrate adds deionized water to 2000g, adds 20g formic acid, is heated to 70 ℃; Get the hybrid metal nitrate solution; Industrial ammonia is mixed with mass ratio with pure water at 1: 1, gets precipitating reagent, precipitating reagent is slowly added to get the hybrid metal nitrate solution, to the pH value be 4, after adding the 20g hydrogen peroxide, continuing to add precipitating reagent to pH value is 9, the insulation 4h; Washing, dehydration; With cerium zirconium based solid solution rare earth oxygen storage material presoma and the 30g laurate after dehydration, shear and disperse, 600 ℃ of lower roasting 5h get described cerium zirconium based solid solution rare earth oxygen storage material.
The specific surface of described cerium zirconium based solid solution rare earth oxygen storage material is 120.02m
2G
-1, getting cerium zirconium based solid solution rare earth oxygen storage material specific surface after 1000 ℃ of roasting 4h is 32.28m
2G
-1, after 1050 ℃ of roasting 12h, specific surface is 24.12m
2G
-1
Above demonstration and described basic principle of the present invention, principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification is principle of the present invention; the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, and these changes and improvements all fall in claimed scope of the present invention.The protection domain that the present invention requires is defined by appending claims and equivalent thereof.
Claims (7)
1. a cerium zirconium based solid solution rare earth oxygen storage material, is characterized in that its specific surface 〉=90m
2G
-1, specific surface 〉=30m after 1000 ℃ of roasting 4h
2G
-1, specific surface 〉=20m after 1050 ℃ of roasting 12h
2G
-1
2. the preparation method of a cerium zirconium based solid solution rare earth oxygen storage material, is characterized in that, it comprises the steps:
(1) preparation of hybrid metal nitrate solution: according to the weight of material component formation and target product, determine the content of cerium oxide, zirconia and other rare earth oxides except cerium, be converted into the weight content of corresponding raw material, cerous nitrate, other rare earth solubility nitrate and zirconium nitrate except cerium is water-soluble, add certain organic acid, get the hybrid metal nitrate solution;
(2) preparation of cerium zirconium based solid solution rare earth oxygen storage material presoma: 1: 1 mixed precipitating reagent of the industrial ammonia with 36% and pure water, slowly join in the hybrid metal nitrate solution of 50-70 ℃, to pH be 3-4, add Ce
3+/ Ce
4+Transform the stoichiometry 1.2-1.5 hydrogen peroxide doubly that needs, continuing to add precipitating reagent is 9 to pH, insulation 2-5h, and washing, dehydration get cerium zirconium based solid solution rare earth oxygen storage material presoma;
(3) surface treatment of cerium zirconium based solid solution rare earth oxygen storage material presoma: cerium zirconium based solid solution rare earth oxygen storage material presoma and certain surfactant are sheared disperseed;
(4) roasting: surface treated cerium zirconium based solid solution rare earth oxygen storage material presoma at 450-800 ℃ of lower roasting 4-8h, is got described cerium zirconium based solid solution rare earth oxygen storage material.
3. preparation method according to claim 2, is characterized in that, described other rare earth solubility nitrate except cerium are selected from one or more the combination in lanthanum nitrate, yttrium nitrate, praseodymium nitrate or neodymium nitrate.
4. preparation method according to claim 2, is characterized in that, described other rare earth solubility nitrate except cerium are selected from nitric acid and lanthana, yittrium oxide, praseodymium oxide or neodymia reaction generate corresponding nitrate solution.
5. preparation method according to claim 2, is characterized in that, in described hybrid metal nitrate solution, the ratio of each nitrate is:
Cerous nitrate 20-70%
Zirconium nitrate 20-70%
Other rare earth solubility nitrate 5-15% except cerium.
6. preparation method according to claim 2, is characterized in that, described organic acid is one or more combination in acetic acid, formic acid or citric acid, and described organic acid addition accounts for the 5-20% of nitrate weight in mixed salt solution by weight.
7. preparation method according to claim 2, it is characterized in that, described surface conditioning agent is selected from laurate, stearic acid or alkenyl succinic anhydride the combination of one or more, and the addition of described surface conditioning agent is counted 30-50% with the weight of described cerium zirconium based solid solution rare earth oxygen storage material.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1241988A (en) * | 1996-12-27 | 2000-01-19 | 阿南化成株式会社 | Composite zirconium-cerium oxide, process for the preparation thereof, and cocatalyst for cleaning exhaust gas |
| CN1403376A (en) * | 2002-10-15 | 2003-03-19 | 清华大学 | Cerium-base quaternary nano level composite RE oxide and its prepn process |
| CN101200371A (en) * | 2006-12-13 | 2008-06-18 | 上海华明高技术（集团）有限公司 | Composite oxide sosoloid based on cerium oxide and zirconia and method for preparing the same |
| US20090274599A1 (en) * | 2006-02-17 | 2009-11-05 | Rhodia Operations | Catalytic compositions comprising the oxides of zirconium, cerium, yttrium, lanthanum and other rare earths |
-
2011
- 2011-11-23 CN CN201110377617.1A patent/CN103127925B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1241988A (en) * | 1996-12-27 | 2000-01-19 | 阿南化成株式会社 | Composite zirconium-cerium oxide, process for the preparation thereof, and cocatalyst for cleaning exhaust gas |
| CN1403376A (en) * | 2002-10-15 | 2003-03-19 | 清华大学 | Cerium-base quaternary nano level composite RE oxide and its prepn process |
| US20090274599A1 (en) * | 2006-02-17 | 2009-11-05 | Rhodia Operations | Catalytic compositions comprising the oxides of zirconium, cerium, yttrium, lanthanum and other rare earths |
| CN101200371A (en) * | 2006-12-13 | 2008-06-18 | 上海华明高技术（集团）有限公司 | Composite oxide sosoloid based on cerium oxide and zirconia and method for preparing the same |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN104437458B (en) * | 2014-11-12 | 2017-05-17 | 诺轩化学科技（上海）有限公司 | Cerium-zirconium-based composite oxide catalytic material and preparation method thereof |
| CN104492414B (en) * | 2014-12-02 | 2017-01-25 | 上海华明高纳稀土新材料有限公司 | Preparation method of cerium-zirconium based solid solution |
| CN104492415A (en) * | 2014-12-02 | 2015-04-08 | 上海华明高纳稀土新材料有限公司 | Preparation method of cerium-zirconium based solid solution catalytic material |
| CN104492414A (en) * | 2014-12-02 | 2015-04-08 | 上海华明高纳稀土新材料有限公司 | Preparation method of cerium-zirconium based solid solution |
| 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 |
| CN105080530A (en) * | 2015-05-26 | 2015-11-25 | 华东理工大学 | Preparation method for cerium-zirconium composite oxide with high performance |
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