CN102247826A - Cubic phase cerium and zirconium based composite oxide with high specific surface area and preparation method thereof - Google Patents
Cubic phase cerium and zirconium based composite oxide with high specific surface area and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 115
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 90
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title abstract description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title abstract description 10
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 62
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 60
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 34
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 20
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000001376 precipitating effect Effects 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000005245 sintering Methods 0.000 claims abstract description 4
- 239000013049 sediment Substances 0.000 claims description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 34
- 229910004625 Ce—Zr Inorganic materials 0.000 claims description 32
- 238000000352 supercritical drying Methods 0.000 claims description 32
- 229910002651 NO3 Inorganic materials 0.000 claims description 31
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 31
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical group CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 23
- 238000000975 co-precipitation Methods 0.000 claims description 21
- 238000001694 spray drying Methods 0.000 claims description 19
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 17
- 239000003153 chemical reaction reagent Substances 0.000 claims description 17
- 239000004094 surface-active agent Substances 0.000 claims description 17
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- 239000013504 Triton X-100 Substances 0.000 claims description 14
- 229920004890 Triton X-100 Polymers 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000000593 microemulsion method Methods 0.000 claims description 14
- 239000003921 oil Substances 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- 238000001556 precipitation Methods 0.000 claims description 13
- 239000004064 cosurfactant Substances 0.000 claims description 12
- 239000004530 micro-emulsion Substances 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- AYAUBWSUZRFVQO-UHFFFAOYSA-N 2-[2-(4-phenyl-5-sulfanylidene-1h-1,2,4-triazol-3-yl)ethyl]benzo[de]isoquinoline-1,3-dione Chemical compound O=C1C(C=23)=CC=CC3=CC=CC=2C(=O)N1CCC1=NNC(=S)N1C1=CC=CC=C1 AYAUBWSUZRFVQO-UHFFFAOYSA-N 0.000 claims description 8
- 241001272567 Hominoidea Species 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 235000011194 food seasoning agent Nutrition 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 claims description 4
- 229940070765 laurate Drugs 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 241000761427 Boraras micros Species 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 17
- 239000001301 oxygen Substances 0.000 abstract description 17
- 238000003860 storage Methods 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000006104 solid solution Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 31
- 239000008367 deionised water Substances 0.000 description 30
- 229910021641 deionized water Inorganic materials 0.000 description 30
- 239000012298 atmosphere Substances 0.000 description 26
- 239000000839 emulsion Substances 0.000 description 25
- 238000005406 washing Methods 0.000 description 23
- 238000001914 filtration Methods 0.000 description 17
- 239000007789 gas Substances 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- 229910020837 La—Pr Inorganic materials 0.000 description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- PZZOEXPDTYIBPI-UHFFFAOYSA-N 2-[[2-(4-hydroxyphenyl)ethylamino]methyl]-3,4-dihydro-2H-naphthalen-1-one Chemical compound C1=CC(O)=CC=C1CCNCC1C(=O)C2=CC=CC=C2CC1 PZZOEXPDTYIBPI-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 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 description 1
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- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- -1 polyoxy Polymers 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011214 refractory ceramic Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Abstract
The invention discloses a cubic phase cerium and zirconium based composite oxide with high specific surface area. Rare earth elements are doped in the cerium-zirconium composite oxide and are selected from two or three of Pr, Nd and La, wherein the molar ratio of Zr to Ce is (1.8-2.5):1; the molar ratio of Pr to Ce is (0-0.32):1; the molar ratio of Nd to Ce is (0-0.32):1; the molar ratio of La to Ce is (0-0.16):1; and the cerium and zirconium based composite oxide exists in a form of cerium-zirconium solid solution. The invention also discloses a preparation method of the cerium and zirconium based composite oxide. The composite oxide is prepared through different precursor precipitating and drying methods; the method has the advantages of simple reaction process and low requirements on drying equipment; the obtained cerium and zirconium based composite oxide has high specific surface area, high thermal stability and high oxygen storage and discharge capacity; and after sintering is performed at the temperature of 1,000 DEG C for 12 hours, the specific surface area is more than 35m<2>/g, particularly more than 60m<2>/g.
Description
Technical field
The present invention relates to a kind of Ce-Zr based composite oxide and preparation method thereof, be specifically related to cube mutually Ce-Zr based composite oxide and preparation method thereof of a kind of high-specific surface area and high oxygen storage capacity.
Background technology
Cerium-based composite oxides is widely used in heterogeneous catalysis [J. Ka par, et al., Catal. Today 50 (1999) 285 – 298.], polishing agent [V.D. Kosynkin, et al., J. Alloys Compd. 303 – 304 (2000) 421 – 425], refractory ceramics [H. Kaneko, et al., J. Mater. Sci. 43 (2008) 3153 – 3161.], sensor material [G. Neri, et al., Sens. Actuators B 114 (2006) 687 – 695.], fuel cell [A. Atkinson, et al., Nat. Mater. 3 (2004) 17 – 27.] etc. the field, CeO
2Ability with storage and release oxygen, but CeO
2Poor heat stability.At CeO
2The middle Zr that introduces
4+Can improve CeO
2Heat endurance, the cerium zirconium compound oxide of formation has kept good storage oxygen performance and catalytic activity simultaneously.The rare earth elements such as La, Pr, Nd that mix in cerium zirconium compound oxide can further improve its heat endurance and catalytic performance, and improve its specific area.Though there is the Ce-Zr based composite oxide of relevant doping lanthanide series to exist, but the composite oxides specific area that makes is not very high, still have deficiency, for example, patent 200610039260.3 discloses a kind of nanometer composite La-Ce-Zr oxide, comprises the cerium oxide of 20-96%, the zirconia of 10-86% and the lanthana of 5-56% in this oxide.From proportioning as can be seen, the addition content of lanthanum is bigger, and the addition content of lanthanum is crossed the storage oxygen performance that conference influences Ce-Zr based composite oxide.Patent 200910054735.1 discloses a kind of cerium oxide and zirconium oxide based sosoloid catalyst, preparation method and application thereof, this catalyst comprises the zirconia of 50-79.65%, the cerium oxide of 20-49.5%, other element oxides of 0.5-25%, form with solid solution exists, shown in other elements be in lanthanum, neodymium, praseodymium, the yttrium one or more, though disclosing, this catalyst adopt multiple rare earth element to carry out admixture, gained catalyst poor heat stability.
Ce-Zr based composite oxide has developed and multiple preparation method, as: coprecipitation [C.E. Hori, et al., Appl. Catal. B 16 (1998) 105 – 117; S. Letichevsky, et al., Appl. Catal.B 58 (2005) 203 – 210.], solution combustion method [V. Grover, et al., Journal of Alloys and Compounds 457 (2008) 498 – 505.], sol-gal process [L.P. Li, et al., J. Mater. Res. 16 (2001) 3207 – 3213.], micro emulsion method [X.H. Wang, et al., Catal. Today 126 (2007) 412 – 419.] etc., different preparation methods can influence its structure and catalytic performance.Wherein coprecipitation is widely used, and technology is simple, realizes industrialization easily.Coprecipitation prepares the cerium zirconium compound oxide presoma, adopts supercritical drying, high-temperature roasting, can obtain the product [patent CN201010116258.X] of high-ratio surface.Though the technology of prepared with microemulsion reactor Ce-Zr based composite oxide is complicated, the product that obtains has high-ratio surface and resistance to elevated temperatures.The method that Gennari etc. [F. C. Gennari, et al., Appl. Catal. A doi:10.1016/j.apcata.2011.03.022.] adopt micro emulsion method, coprecipitation, co-precipitation and supercritical drying to combine is respectively prepared cerium zirconium sosoloid; Among the patent CN02110041.1, obtain cerium zirconium hydroxide through alkali precipitation, centrifugal dehydration, heat treatment etc., adopt spray-drying, high-temperature roasting to make the cerium zirconium sosoloid of high-ratio surface with cerium colloidal sol and zirconium colloidal sol; Among the patent CN200780005579.9, at least 100 ℃ of following thermal precipitation things in water-bearing media, and add surfactant, the product that high-temperature calcination obtains has enough specific area values.Said method or complex process or final catalyst prod specific area are at high temperature lower.
Summary of the invention
The purpose of this invention is to provide a kind of cube phase Ce-Zr based composite oxide of high-specific surface area, this oxide has high thermal stability, high-specific surface area and high oxygen storage capacity.
Another object of the present invention provides the preparation method of these composite oxides, this method technology uniqueness, and course of reaction is controlled easily, the raw material cheapness, the products obtained therefrom performance is good.
The present invention adds two or three among Pr, Nd, the La in cerium zirconium compound oxide, adopt coprecipitation, micro emulsion method or hydro-thermal method to prepare presoma, adopt high-temperature roasting to obtain cube mutually Ce-Zr based composite oxide of high thermal stability, high-specific surface area and high oxygen storage capacity in conjunction with the method for supercritical drying, spray-drying or common oven dry.Concrete technical scheme is as follows:
A kind of cube phase Ce-Zr based composite oxide of high-specific surface area, it is characterized in that: in cerium zirconium compound oxide, mix rare earth element, described rare earth element is two or three among Pr, Nd and the La, wherein the mol ratio of Zr and Ce is 1.8 ~ 2.5:1, the mol ratio of Pr and Ce is 0 ~ 0.32:1, the mol ratio of Nd and Ce is 0 ~ 0.32:1, and the mol ratio of La and Ce is 0 ~ 0.16:1.Ce-Zr based composite oxide of the present invention exists with the cerium zirconium sosoloid form of cube phase, can be confirmed by XRD figure.
A kind of preparation method of cube phase Ce-Zr based composite oxide of high-specific surface area is characterized in that comprising following method:
(1) adopt in following a, b and the c method any the preparation sediment
A, coprecipitation: Ce, Zr and rare earth element soluble-salt are mixed by proportioning, be made into precursor solution; In precursor solution, drip precipitating reagent to pH be 9 ~ 10, obtain suspension; Suspension leave standstill separate, wash after aging sediment;
B, micro emulsion method: Ce, Zr and rare earth element soluble-salt are mixed by proportioning, be made into precursor solution; The precursor solution that obtains is mixed with surface-active, oil phase, cosurfactant, obtain the presoma microemulsion; Precipitant solution, surfactant, oil phase and cosurfactant are mixed, obtain the precipitating reagent microemulsion; The precipitating reagent microemulsion is slowly dropped in the presoma microemulsion, until precipitation fully, with precipitate and separate, wash sediment;
C, hydro-thermal method: Ce, Zr and rare earth element soluble-salt are mixed by proportioning, be made into precursor solution; In precursor solution, add excessive precipitating reagent, make precipitation fully, obtain suspension; Suspension at 1 ~ 15Mpa, 100 ~ 250 ℃ insulation 1-3h down, is added surfactant therein after the cooling, fully contact, separate then, wash sediment;
(2) sediment that obtains is carried out drying, get presoma;
(3) presoma is carried out roasting, get catalyst.
The used soluble-salt of the present invention has nitrate, sulfate, chloride or ammonium salt, preferably nitrate, and concrete is the nitrate of cerium, zirconium, lanthanum, praseodymium and neodymium; The chlorate of cerium, zirconium, lanthanum, praseodymium and neodymium; The sulfate of cerium and zirconium; Cerous nitrate ammonia etc.Used precipitating reagent is unified to be ammoniacal liquor, NaOH solution or Na
2CO
3Solution, preferred ammoniacal liquor (commercially available common ammoniacal liquor), the concentration of used precipitating reagent there is no big influence to reaction.
The present invention can adopt three kinds of methods to be prepared composite oxides, and the main distinction is in the sedimentary preparation in early stage three kinds of methods are arranged, i.e. coprecipitation, micro emulsion method and hydro-thermal method, and the drying in later stage is identical substantially with roasting process.
For coprecipitation, its step is identical with the general used step of co-precipitation, by the control of suitable pH, makes the catalyst that obtains keep high-specific surface area to the full extent.In the method, precursor solution concentration be there is no much influences to reaction, generally about 0.2mol/L, pH transfers to 9-10 can form precipitation.In order to make precipitation fully, needs leave standstill aging at normal temperatures to suspension, and the time is generally 0-24h, is as the criterion fully with precipitation.In addition, when precipitation separation from reactant liquor, can adopt a kind of realization in suction filtration, press filtration and the centrifugation.
The micro emulsion method is compared with coprecipitation, and the formed precipitation particles size of its presoma is more even.The continuous organic solvent phase and the surfactant film of micelle can strengthen the space steric effect between the particle, improve the dispersive property of particle, in the sediment washing process, preferably adopt absolute ethyl alcohol as washing agent, because the surface tension of absolute ethyl alcohol is lower than the surface tension of water, can reach the purpose that reduces and eliminate reunion.In the method, precursor solution is generally about 0.2mol/L, used surfactant is APES (APE), Triton X-100 or AEO (AEO), Triton X-100 can comprise OP-10, Triton X-100 etc., used cosurfactant is a n-hexyl alcohol, and oil phase is cyclohexane or isooctane.Wherein, precursor solution is 10:0.9 ~ 1.2:1 ~ 1.5:6 ~ 8 with surface-active, oil phase, cosurfactant mixed volume ratio; Precipitating reagent, surfactant, oil phase and cosurfactant mixed volume ratio are 10:0.9 ~ 1.2:1 ~ 1.5:6 ~ 8.
During hydro-thermal method was synthetic, the specific area of product was subjected to the influence of temperature, pressure, need select appropriate condition in the preparation.The heating-up temperature that the present invention selects is 100 ~ 250 ℃, will be higher than 130 ℃ especially, and mode of heating is oil bath, electrical heating etc., and temperature retention time is 1 ~ 3 hour, and the packing ratio of suspension in reactor is 50% ~ 70%, and reaction pressure is 1 ~ 15MPa.After the suspension cooling, add surfactant therein, fully contact with suspension, general 1-2h can form interfacial film, suppresses the agglomeration between the particle, the control high-specific surface area.In the method, the influence of precursor solution concentration is little, generally about 0.2mol/L, surfactant is APES (APE), poly-ethanol octyl phenyl ether, laurate, ethylene glycol or AEO (AEO), and poly-ethanol octyl phenyl ether can comprise OP-10, Triton X-100 etc.The surfactant addition is 5% ~ 120% of a soluble-salt consumption.
The sediment that obtains by above-mentioned three kinds of methods can obtain required catalyst through super-dry, roasting, difference according to preparation sediment method therefor, its suitable drying means is closely not identical yet, drying means of the present invention also comprises three kinds, i.e. supercritical drying, spray drying process and common heating seasoning.The sediment that coprecipitation and micro emulsion method obtain preferably adopts supercritical drying or spray drying process to carry out drying, and the sediment that hydro-thermal method obtains can adopt in supercritical drying, spray drying process and the common seasoning any to carry out drying.
When adopting supercritical drying, at first will be with the water in the abundant displacement precipitation thing of absolute ethyl alcohol, then at 40 ~ 60 ℃, carry out supercritical drying under 8 ~ 18MPa pressure, under super critical condition, kept 5 ~ 8 hours, and slowly emitted gas under the constant temperature, obtain dried presoma.Because supercritical fluid do not have gas-liquid interface, in the supercritical drying process, can not produce the structure that causes by additonal pressure and cave in, can make the product that high-specific surface area, particle diameter are evenly distributed.When adopting spray drying process, intake air temperature is 130 ~ 250 ℃, and air outlet temperature is 100 ~ 120 ℃.Adopt commonly when dry, drying optimum temperature is 70 ~ 120 ℃, 6 ~ 24 hours time.
Sediment can get presoma after washing, drying, presoma is remembered catalyst after roasting, and the sintering temperature wide ranges can be 300 ~ 1100 ℃, and the time is 1 ~ 12 hour, and roasting process can carry out in air or inert gas.The catalyst broad application temperature range of final gained, at high temperature the specific area of gained is still very high.
Further, in order to improve the specific area of Ce-Zr based composite oxide, when the synthetic sediment of coprecipitation, micro emulsion method, hydro-thermal method, can add hydrogen peroxide, hydrogen peroxide can be with Ce
3+Be oxidized to Ce
4+, the specific area of raising end product.Hydrogen peroxide adds with precipitating reagent, and addition is with whole Ce
3+Be oxidized to Ce
4+Be as the criterion, can excessively add, concentration is random, and generally usefulness is commercially available hydrogen peroxide.
Empirical tests, in the prepared with microemulsion reactor provided by the invention, the effect of mix two kinds of rare earth element Pr, Nd is best, and in co-precipitation and the Hydrothermal Preparation, the effect of mix three kinds of rare earth element Pr, Nd and La is best.When the rare earth element that mixes was Pr and Nd, the mol ratio of Zr and Ce was for being preferably 1.8 ~ 2.1:1, and the mol ratio of Pr and Ce is preferably 0.15 ~ 0.32:1, and the mol ratio of Nd and Ce is preferably 0.15 ~ 0.32:1.When the rare earth element that mixes was Pr, Nd and La, the mol ratio of Zr and Ce was preferably 1.8 ~ 2.1:1, and the mol ratio of Pr and Ce is preferably 0.16 ~ 0.32:1, and the mol ratio of Nd and Ce is preferably 0.16 ~ 0.32:1, and the mol ratio of La and Ce is preferably 0.16:1.
The present invention has adjusted the proportioning of cerium and zirconium, and according to the cerium zirconium compound oxide still not enough shortcoming of heat endurance and oxygen storage capacity at high temperature, according to exploring and research, therein further admixture a spot of other rare earth elements except that cerium, be two or three among Pr, Nd and the La, add the high temperature sintering that La can suppress cerium zirconium compound oxide; Add Nd and can make CeO
2Produce more polyoxy room, improve the oxygen ability of storing of cerium zirconium compound oxide; Interpolation Pr can improve oxygen transfer ability and the oxygen buffer capacity of Ce.Though the rare earth element addition is very little, promoted the heat endurance and the oxygen storage capacity of Ce-Zr based composite oxide on the whole.
On the basis of improving the composite oxides proportioning, the present invention also improves the preparation technology of compound, three kinds of methods of concrete employing prepare catalyst, but each method has all adopted the dry technology that cooperates with it to prepare presoma, makes the catalyst that makes more superior on performance.Common improvement by proportioning and technology has obtained Ce-Zr based composite oxide of the present invention.By method of the present invention, the composite oxides of gained have high-specific surface area, high thermal stability and high oxygen storage capacity.Behind the synthetic Ce-Zr based composite oxide presoma of coprecipitation, carry out spray-drying, through 1000 ℃ of roastings 12 hours, specific area was higher than 35m again
2/ g; Carry out supercritical drying, specific area is higher than 45m
2/ g.Behind the synthetic Ce-Zr based composite oxide presoma of micro emulsion method, carry out spray-drying, through 1000 ℃ of roastings 12 hours, specific area was higher than 45m again
2/ g; Carry out supercritical drying, specific area is higher than 60m
2/ g.Behind the synthetic cerium zirconium compound oxide presoma of hydro-thermal method, common oven dry, through 1000 ℃ of roastings 12 hours, specific area was higher than 45m again
2/ g; Carry out spray-drying, specific area is higher than 50m
2/ g; Carry out supercritical drying, specific area is higher than 60m
2/ g.Ce-Zr based composite oxide provided by the invention is at high-purity O
2Oxidation under the middle specified temp, inert gas purge, at 700 ℃, the high-purity H of pulse
2, detect with TCD, obtain the product oxygen storage capacity.Oxygen storage capacity in the time of 700 ℃ is greater than 700 μ molg
-1
Cube phase Ce-Zr based composite oxide of Heat stability is good provided by the present invention, high-specific surface area and preparation method thereof has the following advantages:
(1), adopt the Ce-Zr based composite oxide of coprecipitation, supercritical drying and spray drying method for preparation, course of reaction is controlled easily, the raw material cheapness, dry weak point consuming time is realized suitability for industrialized production easily.
(2), adopt hydro-thermal method synthetic, the oven dry of spending the night, course of reaction is simple, and is low to the drying equipment requirement, realizes industrialization easily.
(3), coprecipitation and Hydrothermal Preparation Ce-Zr based composite oxide presoma be through 1000 ℃ of roastings 12 hours, specific area is greater than 35m
2/ g, more particularly, greater than 50m
2/ g.Prepared with microemulsion reactor Ce-Zr based composite oxide presoma through 12 hours specific surfaces of 1000 ℃ of roastings greater than 45m
2/ g, more particularly, greater than 60m
2/ g, resistance to elevated temperatures is good, high-specific surface area and high oxygen storage capacity.
(4), Ce-Zr based composite oxide has high-ratio surface, high thermal stability and height and stores the oxygen ability, can be widely used in fields such as oil, chemical industry, environmental protection, especially is applied to cleaning catalyst for tail gases of automobiles and other catalysis aspects.
Description of drawings
Fig. 1 is the XRD spectra of the embodiment of the invention 1 products obtained therefrom.
Fig. 2 is the XRD spectra of micro emulsion method embodiment 19 products obtained therefroms of the present invention.
Fig. 3 is the XRD spectra of hydro-thermal method embodiment 28 products obtained therefroms of the present invention.
The specific embodiment
Below, by specific embodiment the present invention is set forth, should be understood that following explanation only is in order to explain the present invention, its content not to be limited.
Adopt coprecipitation to prepare Ce-Zr based composite oxide
Embodiment 1
Mol ratio by Ce, Zr, Pr, Nd is 1:2:0.23:0.25, the nitrate of Ce, Zr, Pr, Nd is dissolved in the deionized water, after stirring, the salting liquid of concentration 0.2 mol/L.To mixed solution and dripping ammoniacal liquor to pH be 9 ~ 10, obtain filter cake with the deionized water filtering and washing to pH=7; Filter cake is transferred in the beaker, poured into absolute ethyl alcohol afterwards, the beaker liquid level need be higher than filter cake, leaves standstill after the stirring, and suction filtration obtains the sediment after absolute ethyl alcohol exchanges again, carries out supercritical drying, and super critical condition is 50 ℃, pressure 10MPa; Under super critical condition, kept 5 hours, slowly emit gas under the constant temperature, obtain Ce-Zr-Pr-Nd composite oxides presoma; With Ce-Zr-Pr-Nd composite oxides presoma in air atmosphere 1000 ℃ handled 12 hours, promptly get Ce-Zr-Pr-Nd composite oxides, its specific area is 50.1 m
2/ g.As can be seen from Figure 1, the Ce-Zr-Pr-Nd composite oxides exist with a cube phase cerium zirconium sosoloid form.
Embodiment 2
Mol ratio by Ce, Zr, Pr, Nd is 1:1.8:0.32:0.32, the nitrate of Ce, Zr, Pr, Nd is dissolved in the deionized water, after stirring, to mixed solution and dripping ammoniacal liquor to pH be 9 ~ 10, centrifuge washing carries out centrifugal spray drying to pH=7, and intake air temperature is 130 ~ 250 ℃, air outlet temperature is 100 ~ 120 ℃, obtains Ce-Zr-Pr-Nd composite oxides presoma; With Ce-Zr-Pr-Nd composite oxides presoma in air atmosphere 1000 ℃ handled 12 hours, promptly get Ce-Zr-Pr-Nd composite oxides, its specific area is 38.2 m
2/ g.With Ce-Zr-Pr-Nd composite oxides presoma at N
2Handled 12 hours for 1000 ℃ in the atmosphere, promptly get Ce-Zr-Pr-Nd composite oxides, its specific area is 41.5 m
2/ g.
Embodiment 3
Mol ratio by Ce, Zr, Pr, Nd, La is 1:2:0.2:0.21:0.16, the nitrate of Ce, Zr, Pr, Nd, La is dissolved in the deionized water, after stirring, be 9 ~ 10 to mixed solution and dripping ammoniacal liquor to pH, usefulness deionized water filtering and washing is to pH=7; With the water in the absolute ethyl alcohol exchange sediment.Carry out supercritical drying, super critical condition is 50 ℃, pressure 15MPa; Under super critical condition, kept 5 hours, slowly emit gas under the constant temperature, obtain Ce-Zr-Pr-Nd-La composite oxides presoma; With the 550 ℃ of roastings 2 hours in air atmosphere of Ce-Zr-Pr-Nd-La composite oxides presoma, its specific area is 174.5 m
2/ g.. handled 12 hours for 1000 ℃ in air atmosphere, promptly get Ce-Zr-Pr-Nd-La composite oxides, its specific area is 54.3 m
2/ g.
Embodiment 4
With embodiment 3 identical operations, difference is: the mol ratio of Ce, Zr, Pr, Nd, La is 1:2:0.2:0.1:0.16, and the specific area of gained composite oxides is 51.1 m
2/ g.
Embodiment 5
With embodiment 3 identical operations, difference is: the mol ratio of Ce, Zr, Pr, Nd, La is 1:1.8:0.1:0.32:0.16, and the specific area of gained composite oxides is 50.2m
2/ g.
Embodiment 6
With embodiment 1 identical operations, difference is: room temperature left standstill aging 10 hours, with Ce-Zr-Pr-Nd composite oxides presoma in air atmosphere 1000 ℃ handled 12 hours, promptly get the Ce-Zr-Pr-Nd composite oxides, its specific area is 49.8m
2/ g.
Embodiment 7
With embodiment 1 identical operations, difference is: dropping ammonia generates post precipitation, drips an amount of hydrogen peroxide, with Ce-Zr-Pr-Nd composite oxides presoma in air atmosphere 1000 ℃ handled 12 hours, promptly get Ce-Zr-Pr-Nd composite oxides, its specific area is 55.5m
2/ g.
Embodiment 8
With embodiment 1 identical operations, difference is: precipitating reagent is the NaOH solution of 1mol/L, with Ce-Zr-Pr-Nd composite oxides presoma in air atmosphere 1000 ℃ handled 12 hours, promptly get the Ce-Zr-Pr-Nd composite oxides, its specific area is 47.5 m
2/ g.
Embodiment 9
With embodiment 1 identical operations, difference is: precipitating reagent is the Na of 1mol/L
2CO
3, with Ce-Zr-Pr-Nd composite oxides presoma in air atmosphere 1000 ℃ handled 12 hours, promptly get the Ce-Zr-Pr-Nd composite oxides, its specific area is 43.2 m
2/ g.
Embodiment 10
With embodiment 1 identical operations, difference is: adopt centrifugation to obtain sediment, water in the absolute ethyl alcohol displacement precipitation thing, after carrying out supercritical drying, with Ce-Zr-Pr-Nd composite oxides presoma in air atmosphere 1000 ℃ handled 12 hours, promptly get Ce-Zr-Pr-Nd composite oxides, its specific area is 52.7m
2/ g.
Embodiment 11
Mol ratio by Ce, Zr, La, Nd is 1:2.5:0.1:0.2, the chlorate of Ce, Zr, La, Nd is dissolved in the deionized water, after stirring, to mixed solution and dripping ammoniacal liquor to pH be 9 ~ 10, obtain sediment with the deionized water filtering and washing to pH=7, the water with in the absolute ethyl alcohol exchange sediment carries out supercritical drying, super critical condition is 40 ℃, pressure 18MPa; Under super critical condition, kept 6 hours, slowly emit gas under the constant temperature, obtain Ce-Zr-La-Nd composite oxides presoma; With Ce-Zr-La-Nd composite oxides presoma in air atmosphere 1000 ℃ handled 12 hours, promptly get the Ce-Zr-La-Nd composite oxides, its specific area is 45.1 m
2/ g.
Mol ratio by Ce, Zr, La, Pr is 1:2.5:0.1:0.19, the chlorate of Ce, Zr, La, Pr is dissolved in the deionized water, after stirring, to mixed solution and dripping ammoniacal liquor to pH be 9 ~ 10, obtain sediment with the deionized water filtering and washing to pH=7, the water with in the absolute ethyl alcohol exchange sediment carries out supercritical drying, super critical condition is 60 ℃, pressure 8MPa; Under super critical condition, kept 6 hours, slowly emit gas under the constant temperature, obtain Ce-Zr-La-Pr composite oxides presoma; With Ce-Zr-La-Pr composite oxides presoma in air atmosphere 1000 ℃ handled 12 hours, promptly get the Ce-Zr-La-Nd composite oxides, its specific area is 47.8 m
2/ g.
Embodiment 13
Mol ratio by Ce, Zr, Pr, Nd, La is 1:2:0.22:0.23:0.16, the nitrate of Ce, Zr, Pr, Nd, La is dissolved in the deionized water, after stirring, be 9 ~ 10 to mixed solution and dripping ammoniacal liquor and hydrogen peroxide to pH, usefulness deionized water centrifuge washing is to pH=7; Water with in the absolute ethyl alcohol exchange sediment carries out supercritical drying, and super critical condition is 50 ℃, pressure 15MPa; Under super critical condition, kept 5 hours, slowly emit gas under the constant temperature, obtain Ce-Zr-Pr-Nd-La composite oxides presoma; Handled 12 hours for 1000 ℃ in air atmosphere, promptly get the Ce-Zr-Pr-Nd-La composite oxides, its specific area is 59.3 m
2/ g.
Embodiment 14
With embodiment 13 identical operations, difference is: the mol ratio of Ce, Zr, Pr, Nd, La is 1:1.8:0.32:0.23:0.16, and the composite oxides specific area is 62.6 m
2/ g.
Embodiment 15
With embodiment 13 identical operations, difference is: the mol ratio of Ce, Zr, Pr, Nd, La is 1:1.8:0.32:0.3:0.16, and the composite oxides specific area is 63.2 m
2/ g.
Embodiment 16
With embodiment 11 identical operations, difference is: after obtaining sediment, carry out centrifugal spray drying (intake air temperature 200-220 ℃, 100 ~ 120 ℃ of air outlet temperatures), obtain Ce-Zr-Pr-Nd-La composite oxides presoma; Handled 12 hours for 1000 ℃ in air atmosphere, promptly get the Ce-Zr-Pr-Nd-La composite oxides, its specific area is 43.3 m
2/ g.
Embodiment 17
Mol ratio by Ce, Zr, Pr, Nd, La is 1:2.1:0.2:0.19:0.11, with Ce (NH
4)
2(NO
3)
62H
2O, Zr (SO
4)
24H
2The nitrate of O and Pr, Nd, La is dissolved in the deionized water, after stirring, is 9 ~ 10 to mixed solution and dripping ammoniacal liquor to pH, and usefulness deionized water centrifuge washing is to pH=7; With the water in the absolute ethyl alcohol exchange sediment.Carry out supercritical drying, super critical condition is 50 ℃, pressure 15MPa; Under super critical condition, kept 5 hours, slowly emit gas under the constant temperature, obtain Ce-Zr-Pr-Nd-La composite oxides presoma; Handled 12 hours for 1000 ℃ in air atmosphere, promptly get the Ce-Zr-Pr-Nd-La composite oxides, its specific area is 50.6 m
2/ g.
Embodiment 18
Mol ratio by Ce, Zr, Pr, Nd, La is 1:2.5:0.19:0.18:0.10, with Ce (SO
4)
24H
2O, Zr (SO
4)
24H
2The nitrate of O and Pr, Nd, La is dissolved in the deionized water, after stirring, is 9 ~ 10 to mixed solution and dripping ammoniacal liquor to pH, and usefulness deionized water centrifuge washing is to pH=7; With the water in the absolute ethyl alcohol exchange sediment.Carry out supercritical drying, super critical condition is 50 ℃, pressure 15MPa; Under super critical condition, kept 5 hours, slowly emit gas under the constant temperature, obtain Ce-Zr-Pr-Nd-La composite oxides presoma; Handled 12 hours for 1000 ℃ in air atmosphere, promptly get the Ce-Zr-Pr-Nd-La composite oxides, its specific area is 47.3 m
2/ g.
Adopt the prepared with microemulsion reactor Ce-Zr based composite oxide
Embodiment 19
Mol ratio by Ce, Zr, Pr, Nd and La is the nitrate of 1:2:0.17:0.18:0.05 with Ce, Zr, Pr, Nd and La, is dissolved in the deionized water, stirs; Prepare two parts of emulsions, the nitrate solution of emulsion one: Ce, Zr, Pr, Nd and La, Triton X-100, cyclohexane and n-hexyl alcohol; Emulsion two: ammoniacal liquor, hydrogen peroxide, Triton X-100, cyclohexane and n-hexyl alcohol.Precursor solution is 10:0.9 ~ 1.2:1 ~ 1.5:6 ~ 8 with surface-active, oil phase, cosurfactant mixed volume ratio.Precipitant solution, surfactant, oil phase and cosurfactant mixed volume ratio are 10:0.9 ~ 1.2:1 ~ 1.5:6 ~ 8.Emulsion two slowly is added drop-wise in the emulsion one, uses the deionized water filtering and washing, washes with alcohol again; Exchange water in Ce, Zr and the RE sediment with absolute ethyl alcohol; Sediment after the ethanol exchange is carried out supercritical drying, and super critical condition is 40 ℃, pressure 15MPa; Under super critical condition, kept 6 hours, slowly emit gas under the constant temperature, obtain Ce-Zr-Pr-Nd-La composite oxides presoma; Again with Ce-Zr-Pr-Nd-La composite oxides presoma in air atmosphere 1000 ℃ handled 12 hours, promptly get the Ce-Zr-Pr-Nd-La composite oxides, its specific area is 58.7m
2/ g.Obtaining the Ce-Zr-Pr-Nd-La composite oxides from Fig. 2 exists with a cube phase cerium zirconium sosoloid form.
With embodiment 19 identical operations, difference is: surfactant is APE, the Ce-Zr-Pr-Nd-La composite oxides presoma that obtains in air atmosphere 1000 ℃ handled 12 hours, its specific area is 57.1m
2/ g.
Embodiment 21
Mol ratio by Ce, Zr, Pr and Nd is the nitrate of 1:2.1:0.25:0.26 with Ce, Zr, Pr and Nd, is dissolved in the deionized water, stirs; Prepare two parts of emulsions, the nitrate solution of emulsion one: Ce, Zr, Pr, Nd, Triton X-100, cyclohexane and n-hexyl alcohol; Emulsion two: ammoniacal liquor, hydrogen peroxide, Triton X-100, cyclohexane and n-hexyl alcohol.Emulsion two slowly is added drop-wise in the emulsion one, uses the deionized water filtering and washing, washes with alcohol again; Exchange water in Ce, Zr, Pr, the Nd sediment with absolute ethyl alcohol; Sediment after the ethanol exchange is carried out supercritical drying, and super critical condition is 50 ℃, pressure 15MPa; Under super critical condition, kept 5 hours, slowly emit gas under the constant temperature, obtain Ce-Zr-Pr-Nd composite oxides presoma; With Ce-Zr-Pr-Nd composite oxides presoma in air atmosphere 550 ℃ handled 2 hours, promptly get Ce-Zr-Pr-Nd composite oxides, its specific area is 198.6 m
2/ g; Through 1000 ℃ of roastings after 12 hours, its specific area is 63.2m in air atmosphere
2/ g.
Embodiment 22
With embodiment 21 identical operations, difference is: the mol ratio of Ce, Zr, Pr and Nd is 1:2.1:0.28:0.23, the Ce-Zr-Pr-Nd composite oxides presoma that obtains in air atmosphere 1000 ℃ handled 12 hours, its specific area is 65.0m
2/ g.
Embodiment 23
With embodiment 21 identical operations, difference is: after obtaining sediment, carry out (intake air temperature 180-200 ℃ of centrifugal spray drying, 100 ~ 120 ℃ of air outlet temperatures), the Ce-Zr-Pr-Nd composite oxides presoma that obtains in air atmosphere 1000 ℃ handled 12 hours, its specific area is 50.7m
2/ g.
Embodiment 24
Mol ratio by Ce, Zr, La and Nd is the nitrate of 1:2.5:0.08:0.26 with Ce, Zr, La and Nd, is dissolved in the deionized water, stirs; Prepare two parts of emulsions, the nitrate solution of emulsion one: Ce, Zr, La, Nd, Triton X-100, cyclohexane and n-hexyl alcohol; Emulsion two: ammoniacal liquor, hydrogen peroxide, Triton X-100, cyclohexane and n-hexyl alcohol.Emulsion two slowly is added drop-wise in the emulsion one, uses the deionized water filtering and washing, washes with alcohol again; Exchange water in Ce, Zr, La, the Nd sediment with absolute ethyl alcohol; Sediment after the ethanol exchange is carried out supercritical drying, and super critical condition is 50 ℃, pressure 15MPa; Under super critical condition, kept 5 hours, slowly emit gas under the constant temperature, obtain Ce-Zr-La-Nd composite oxides presoma; Again with Ce-Zr-La-Nd composite oxides presoma in air atmosphere 1000 ℃ handled 12 hours, promptly get the Ce-Zr-La-Nd composite oxides, its specific area is 53.2m
2/ g.
Embodiment 25
Mol ratio by Ce, Zr, La and Pr is the chlorate of 1:2.5:0.08:0.26 with Ce, Zr, La and Pr, is dissolved in the deionized water, stirs; Prepare two parts of emulsions, the nitrate solution of emulsion one: Ce, Zr, La, Pr, AEO, cyclohexane and n-hexyl alcohol; Emulsion two: ammoniacal liquor, hydrogen peroxide, AEO, isooctane and n-hexyl alcohol.Emulsion two slowly is added drop-wise in the emulsion one, uses the deionized water filtering and washing, washes with alcohol again; Exchange water in Ce, Zr, La, the Pr sediment with absolute ethyl alcohol; Sediment after the ethanol exchange is carried out supercritical drying, and super critical condition is 50 ℃, pressure 15MPa; Under super critical condition, kept 5 hours, slowly emit gas under the constant temperature, obtain Ce-Zr-La-Pr composite oxides presoma; Again with Ce-Zr-La-Pr composite oxides presoma in air atmosphere 1000 ℃ handled 12 hours, promptly get the Ce-Zr-La-Pr composite oxides, its specific area is 54.1m
2/ g.
Embodiment 26
Mol ratio by Ce, Zr, Pr and Nd is the nitrate of 1:2:0.32:0.32 with Ce, Zr, Pr and Nd, is dissolved in the deionized water, stirs; Prepare two parts of emulsions, the nitrate solution of emulsion one: Ce, Zr, Pr, Nd, Triton X-100, cyclohexane and n-hexyl alcohol; Emulsion two: ammoniacal liquor, hydrogen peroxide, Triton X-100, isooctane and n-hexyl alcohol.Emulsion two slowly is added drop-wise in the emulsion one, uses the deionized water filtering and washing, washes with alcohol again; Exchange water in Ce, Zr, Pr, the Nd sediment with absolute ethyl alcohol; Sediment after the ethanol exchange is carried out supercritical drying, and super critical condition is 60 ℃, pressure 13MPa; Under super critical condition, kept 5 hours, slowly emit gas under the constant temperature, obtain Ce-Zr-Pr-Nd composite oxides presoma; Through 1000 ℃ of roastings after 12 hours, its specific area is 66.7m in air atmosphere
2/ g.
Embodiment 27
With embodiment 26 identical operations, difference is: after obtaining sediment, carry out centrifugal spray drying (intake air temperature 220-250 ℃, 100 ~ 120 ℃ of air outlet temperatures), obtain Ce-Zr-Pr-Nd composite oxides presoma; Through 1000 ℃ of roastings after 12 hours, its specific area is 52m in air atmosphere
2/ g.
The Hydrothermal Preparation Ce-Zr based composite oxide
Embodiment 28
Mol ratio by Ce, Zr, Pr, Nd is 1:2:0.23:0.25, the nitrate of Ce, Zr, Pr, Nd is dissolved in the deionized water, stir, with acclimatization agent and hydrogen peroxide mixing, obtain suspension, transfer to (still pressure 1 ~ 15Mpa) in the autoclave, stir down, 200 ℃ are incubated 1.5 hours, obtain sediment, after the cooling, open autoclave, add an amount of laurate, addition is 15% of a nitrate total amount, stirs, sediment is carried out filtration washing, obtain presoma, the 100-120 ℃ of oven dry of spending the night obtains dried presoma; Presoma 1000 ℃ of roastings 12 hours, is obtained the Ce-Zr-Pr-Nd composite oxides, and its specific area is 49.2 m
2/ g.Obtaining the Ce-Zr-Pr-Nd composite oxides from Fig. 3 exists with a cube phase cerium zirconium sosoloid form.
Embodiment 29
With embodiment 28 identical operations, difference is: 160 ℃ are incubated 2 hours, and presoma 1000 ℃ of roastings 12 hours, is obtained the Ce-Zr-Pr-Nd composite oxides, and its specific area is 45.1 m
2/ g.
Embodiment 30
With embodiment 28 identical operations, difference is: carry out spray-drying (130 ~ 150 ℃ of intake air temperature, 100 ~ 120 ℃ of air outlet temperatures), presoma 1000 ℃ of roastings 12 hours, is obtained the Ce-Zr-Pr-Nd composite oxides, its specific area is 53.4m
2/ g.
Embodiment 31
With embodiment 28 identical operations, difference is: carry out supercritical drying, presoma 1000 ℃ of roastings 12 hours, is obtained the Ce-Zr-Pr-Nd composite oxides, its specific area is 62.5m
2/ g.
Embodiment 32
With embodiment 28 identical operations, difference is: add proper amount of glycol, addition is 100% of a nitrate total amount, stir, sediment is carried out filtration washing, obtains presoma, with presoma 1000 ℃ of roastings 12 hours, obtain the Ce-Zr-Pr-Nd composite oxides, its specific area is 49.8m
2/ g.
Embodiment 33
With embodiment 28 identical operations, difference is: add an amount of APE, addition is 10% of a nitrate total amount, stir, sediment is carried out filtration washing, obtains presoma, with presoma 1000 ℃ of roastings 12 hours, obtain the Ce-Zr-Pr-Nd composite oxides, its specific area is 45.3m
2/ g.
Embodiment 34
Press Ce, Zr, Pr, the mol ratio of Nd and La is that 1:2:0.17:0.18:0.05 is with Ce, Zr, Pr, the nitrate of Nd and La, be dissolved in the deionized water, stir, with acclimatization agent and hydrogen peroxide mixing, obtain suspension, transfer to (still is pressed 10Mpa) in the autoclave, stir down, 250 ℃ are incubated 2 hours, obtain sediment, after the cooling, open autoclave, add proper amount of glycol, addition is 120% of a nitrate total amount, stirs, sediment is carried out filtration washing, obtain presoma, 100 ℃ of oven dry of spending the night obtain dried presoma; Presoma 1000 ℃ of roastings 12 hours, is obtained Ce-Zr-Pr-Nd-La composite oxides, and its specific area is 50.8m
2/ g.
Embodiment 35
Press Ce, Zr, Pr, the mol ratio of Nd and La is that 1:2:0.16:0.16:0.16 is with Ce, Zr, Pr, the nitrate of Nd and La, be dissolved in the deionized water, stir, with acclimatization agent and hydrogen peroxide mixing, obtain suspension, transfer to (still is pressed 1Mpa) in the autoclave, stir down, 100 ℃ are incubated 3 hours, obtain sediment, after the cooling, open autoclave, add an amount of laurate, addition is 30% of a nitrate total amount, stirs, sediment is carried out filtration washing, obtain presoma, the 100-120 ℃ of oven dry of spending the night obtains dried presoma; Presoma 1000 ℃ of roastings 12 hours, is obtained Ce-Zr-Pr-Nd-La composite oxides, and its specific area is 45.4m
2/ g.
Embodiment 36
With embodiment 35 identical operations, difference is: 200 ℃ are incubated 3 hours, and presoma 1000 ℃ of roastings 12 hours, is obtained Ce-Zr-Pr-Nd-La composite oxides, and its specific area is 54 m
2/ g.
Embodiment 37
Mol ratio by Ce, Zr, La and Pr is the nitrate of 1:2.5:0.08:0.26 with Ce, Zr, La and Pr, be dissolved in the deionized water, stir, with acclimatization agent and hydrogen peroxide mixing, obtain suspension, transfer to (still is pressed 15Mpa) in the autoclave, stir down, 150 ℃ are incubated 2 hours, obtain sediment, after the cooling, open autoclave, add OP-10 or Triton X-100, addition is 35% of a nitrate total amount, stirs, sediment is carried out filtration washing, obtain presoma, the 70-80 ℃ of oven dry of spending the night obtains dried presoma; Presoma 1000 ℃ of roastings 12 hours, is obtained Ce-Zr-La-Pr composite oxides, and its specific area is 47.1m
2/ g.
Embodiment 38
Being 1:2.5:0.09:0.25 by the mol ratio of Ce, Zr, La and Nd is dissolved in the nitrate of Ce, Zr, La and Nd in the deionized water, stir, with acclimatization agent and hydrogen peroxide mixing, obtain suspension, transfer in the autoclave, stir down, 150 ℃ are incubated 2 hours, obtain sediment, after the cooling, open autoclave, add an amount of AEO, addition is 40% of a nitrate total amount, stir, sediment is carried out filtration washing, obtain presoma, 100 ℃ of oven dry of spending the night obtain dried presoma; Presoma 1000 ℃ of roastings 12 hours, is obtained the Ce-Zr-La-Nd composite oxides, and its specific area is 45.5m
2/ g.
Claims (10)
1. cube phase Ce-Zr based composite oxide of a high-specific surface area, it is characterized in that: in cerium zirconium compound oxide, mix rare earth element, described rare earth element is two or three among Pr, Nd and the La, wherein the mol ratio of Zr and Ce is 1.8～2.5:1, the mol ratio of Pr and Ce is 0～0.32:1, the mol ratio of Nd and Ce is 0～0.32:1, and the mol ratio of La and Ce is 0～0.16:1; Described Ce-Zr based composite oxide exists with the form of cerium zirconium sosoloid.
2. according to claim 1 cube of phase Ce-Zr based composite oxide, it is characterized in that: the rare earth element that mixes is Pr and Nd, the mol ratio of Zr and Ce is 1.8～2.1:1, and the mol ratio of Pr and Ce is 0.15～0.32:1, and the mol ratio of Nd and Ce is 0.15～0.32:1.
3. according to claim 1 cube of phase Ce-Zr based composite oxide, it is characterized in that: the rare earth element that mixes is Pr, Nd and La, the mol ratio of Zr and Ce is 1.8～2.1:1, the mol ratio of Pr and Ce is 0.16～0.32:1, the mol ratio of Nd and Ce is 0.16～0.32:1, and the mol ratio of La and Ce is 0.16:1.
4. the preparation method of cube phase Ce-Zr based composite oxide of the described high-specific surface area of claim 1 is characterized in that may further comprise the steps:
(1) adopt in following a, b and the c method any the preparation sediment
A. coprecipitation: Ce, Zr and rare earth element soluble-salt are mixed by proportioning, be made into precursor solution; In precursor solution, drip precipitating reagent to pH be 9～10, obtain suspension; Suspension leave standstill separate, wash after aging sediment;
B. micro emulsion method: Ce, Zr and rare earth element soluble-salt are mixed by proportioning, be made into precursor solution; The precursor solution that obtains is mixed with surface-active, oil phase, cosurfactant, obtain the presoma microemulsion; Precipitant solution, surfactant, oil phase and cosurfactant are mixed, obtain the precipitating reagent microemulsion; The precipitating reagent microemulsion is slowly dropped in the presoma microemulsion, until precipitation fully, with precipitate and separate, wash sediment;
C. hydro-thermal method: Ce, Zr and rare earth element soluble-salt are mixed by proportioning, be made into precursor solution; In precursor solution, add excessive precipitating reagent, make precipitation fully, obtain suspension; Suspension at 1～15Mpa, 100～250 ℃ insulation 1-3h down, is added surfactant therein after the cooling, fully contact, separate then, wash sediment;
(2) sediment that obtains is carried out drying, get presoma;
(3) presoma is carried out roasting, get catalyst.
5. preparation method according to claim 4 is characterized in that: in the step (2), it is supercritical drying, spray drying process or common seasoning that sediment is carried out dry method; The condition of supercritical drying is: with the water in the absolute ethyl alcohol exchange sediment, then with sediment at 40～60 ℃, carry out supercritical drying under 8～18MPa, kept 5～8 hours; The condition of spray drying process is: 130～250 ℃ of intake air temperature, 100～120 ℃ of air outlet temperatures; The condition of common seasoning is: 70～120 ℃ of baking temperatures, 6～24 hours time.
6. preparation method according to claim 5, it is characterized in that: the sediment that coprecipitation and micro emulsion method obtain adopts supercritical drying or spray drying process to carry out drying, and any in sediment employing supercritical drying, spray drying process and the common seasoning that hydro-thermal method obtains carries out drying.
7. preparation method according to claim 4 is characterized in that: in the step (1), the soluble-salt of Ce, Zr and rare earth element is nitrate, sulfate, chloride or ammonium salt; Precipitating reagent is ammoniacal liquor, NaOH solution or Na
2CO
3Solution; Join the concentration of precursor solution be 0.2mol/L; In the step (3), roasting process carries out in air or inert gas, and sintering temperature is 300～1100 ℃, and roasting time is 1～12 hour.
8. preparation method according to claim 4 is characterized in that: in coprecipitation, micro emulsion method and the hydro-thermal method, also be added with hydrogen peroxide in precipitating reagent, with Ce
3+Be oxidized to Ce
4+
9. preparation method according to claim 4 is characterized in that: in the micro emulsion method, surfactant is APES, Triton X-100 or AEO, and cosurfactant is a n-hexyl alcohol, and oil phase is cyclohexane or isooctane; Precursor solution is 10:0.9～1.2:1～1.5:6～8 with surface-active, oil phase, cosurfactant mixed volume ratio; Precipitating reagent, surfactant, oil phase and cosurfactant mixed volume ratio are 10:0.9～1.2:1～1.5:6～8.
10. preparation method according to claim 4 is characterized in that: in the hydro-thermal method, surfactant is APES, poly-ethanol octyl phenyl ether, laurate, ethylene glycol or AEO; The surfactant addition is 5%～120% of a soluble-salt consumption.
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