CN101992083A - Composite cerium-zirconium solid solution with high oxygen storage capability and preparation method thereof - Google Patents
Composite cerium-zirconium solid solution with high oxygen storage capability and preparation method thereof Download PDFInfo
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- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 title claims abstract description 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000001301 oxygen Substances 0.000 title claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 title claims abstract description 9
- 239000006104 solid solution Substances 0.000 title abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 28
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 23
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000004094 surface-active agent Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 24
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 claims description 13
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 claims description 13
- 229910002651 NO3 Inorganic materials 0.000 claims description 12
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 239000013049 sediment Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 7
- 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 6
- 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 6
- 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 6
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 3
- 230000006798 recombination Effects 0.000 claims description 3
- 238000005215 recombination Methods 0.000 claims description 3
- 235000015096 spirit Nutrition 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 8
- 238000000746 purification Methods 0.000 abstract description 2
- 230000002441 reversible effect Effects 0.000 abstract description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract 2
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract 2
- 238000000975 co-precipitation Methods 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 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 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910052779 Neodymium Inorganic materials 0.000 description 6
- 229910052777 Praseodymium Inorganic materials 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 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 description 4
- 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 description 4
- 238000012360 testing method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- XQTIWNLDFPPCIU-UHFFFAOYSA-N cerium(3+) Chemical compound [Ce+3] XQTIWNLDFPPCIU-UHFFFAOYSA-N 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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Abstract
The invention relates to composite cerium-zirconium solid solution with high oxygen storage capability and a preparation method thereof. The method for preparing the composite cerium-zirconium solid solution is characterized in that: the oxygen storage capability of the product is improved by adopting a cheap surfactant. The composite cerium-zirconium solid solution is compounded by cerium oxide, zirconium oxide and auxiliary agent; the surfactant capable of improving the oxygen storage capability is added during compounding; the solid solution comprises the following components in percentage by weight: based on composite oxides, 10 to 80 percent of cerium oxide, 10 to 70 percent of zirconium oxide and 10 to 20 percent of auxiliary agent; the solid solution is prepared by adopting a reverse co-precipitation method, and after being roasted at about 700 DEG C, a sample without the surfactant has the oxygen storage capability of 630 mol CO/g at 400 DEG C, and a sample adopting the surfactant has the oxygen storage capability of over 900 mol CO/g at 400 DEG C. The composite cerium-zirconium solid solution is mainly used for a carrier and an auxiliary agent of a motor vehicle exhaust purification catalyst.
Description
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Technical field:
The present invention relates to compound cerium zirconium sosoloid and preparation method thereof field.More particularly, relate to as the purifying vehicle exhaust gas catalyst with the compound cerium zirconium sosoloid of carrier and auxiliary agent and preparation method thereof field.
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Background technology:
Automobile exhausting is the primary pollution source of current atmosphere, the HC of its discharging, CO, NO
x, directly harm humans is healthy, and environment is worked the mischief.More and more strict emission control standards has all been worked out in countries in the world, and has spent discharging and pollution that a large amount of manpower and materials and financial resources are administered motor-vehicle tail-gas.With regard to China, present stage has entered the emission request of popularizing state 4.
The most effectual way of automobile exhausting pollutant control is to adopt the external purification catalyst, as three-way catalyst.The cerium oxide constituent element is as one of important composition in the three-way catalyst, its Ce
4+Ce
3+Reversible process provides the abundant oxygen ability of storing for catalyst.The development of cerium oxide develops into the current quaternary or the compound cerium zirconium sosoloid of multicomponent more from initial single constituent element.Single cerium oxide loses rapidly because being easy to sintering and stores the oxygen ability, and the appearance of cerium zirconium sosoloid, has produced abundant crystal boundary phase, has changed the microstructure of hydrogen-storing material from lattice, has promoted the heat endurance of material greatly and has stored the oxygen ability.Thereby cerium zirconium sosoloid, comprise all kinds of compound cerium zirconium sosoloids, become one of focus of present three-way catalyst research field.
In the prior art, Shanghai XX non-ferrous metal company adds zirconia in cerium oxide, and it stores the oxygen ability apparently higher than single cerium oxide, 600 ℃ aging after, its oxygen storage capacity is 0.440mmol/g; 900 ℃ aging after, its oxygen storage capacity is 0.335mmol/g.
China Agricultural University and Beijing Institute of Technology adopt distinct methods to prepare cerium zirconium sosoloid, and the test oxygen storage capacity is 0.106 ~ 0.285mmol/g.
To contain the nitrate aqueous solution of zirconium and cerium (III) and the aqueous solution of carbonic hydroammonium or ammonium carbonate among the CN1369460A, and obtain sediment, oxygen storage capacity is 0.37mmol/g after 500 ℃ of roastings.
Above research worker explores the influence of different preparation methods to properties of product emphatically, the heat endurance and the oxygen storage capacity of gained cerium zirconium sosoloid sample are not high, very inconsiderable, its catalyzed conversion ability remains to be increased substantially, could satisfy as the needs of purifying vehicle exhaust gas catalyst with carrier and auxiliary agent, for reaching related request, automotive emission provides technical guarantee, to reduce HC, CO, the NO in the automotive emission
xContent effectively alleviates the pollution of motor-vehicle tail-gas to atmosphere.
Summary of the invention:
The heat endurance and the oxygen storage capacity of cerium zirconium sosoloid that the present invention is directed to prior art is not high, and it is not enough that its catalyzed conversion ability remains to be increased substantially etc., and its objective is provides a kind of compound cerium zirconium sosoloid for preparing high oxygen storage power.
The compound cerium zirconium sosoloid of a kind of high oxygen storage power, it is characterized in that mainly by cerium oxide, zirconia and
Auxiliary agent is composited, and adds the surfactant that can improve oxygen storage capacity in the preparation recombination process; The percentage by weight of its component constitutes, and with the composite oxides metering is cerium oxide 10 ~ 80%, zirconia 10 ~ 70%, auxiliary agent 10 ~ 20%; Described auxiliary agent is at least a in lanthana, neodymia, praseodymium oxide, the yittrium oxide, or wherein any two kinds, three kinds, the four kinds mixtures that mix to obtain with arbitrary proportion; Described surfactant is any one among polyethylene glycol PEG200, PEG2000, the PEG20000, or mix with arbitrary proportion for wherein two kinds, three kinds, or be PVA, or be PVA with polyethylene glycol PEG200, PEG2000, PEG20000 in any one or two kinds or three kinds mix with arbitrary proportion; Consumption be in the solution oxide aggregate 10 ~ 30%.
Further feature is: described cerium oxide percentage by weight is 45-60%, and described zirconia percentage by weight is 30-45%.
Said auxiliary agent is neodymia and praseodymium oxide.
Said auxiliary agent weight content is 8 ~ 14%.
The preparation method of the compound cerium zirconium sosoloid of the present invention is characterized in that cerium oxide, zirconia with metering
Be dissolved in respectively in the nitric acid with auxiliary agent, the solubility nitrate solution that makes mixes the back and is presoma, adds the surfactant of metering in presoma; Under fully stirring precursor solution is added in 50 ℃ ~ 70 ℃ ammonia spirits, it is precipitated fully; Then sediment is incubated the 24 ~ 48h that refluxes in 100 ~ 120 ℃; Behind the suction filtration, roasting direct 2.5-5h in 650-780 ℃ of Muffle furnaces.
The preparation method of compound cerium zirconium sosoloid provided by the invention is: the solubility nitrate precursor solution with cerium, zirconium and auxiliary agent is a raw material, forms according to the weight of target product to be mixed with mixed solution.Add a certain amount of polyethylene glycol PEG20000+PEG200 mixture, stir.Under agitation above-mentioned mixed solution is added dropwise in the preprepared hot ammonia spirit, the rate of addition of control mixed solution, general 10-20mL/min is very important.After treating that precipitation fully, regulate acidity to pH 10.0 with ammoniacal liquor (or other suitable alkaline solutions, alkaline matter).To precipitate together with mother liquor and change 100 ~ 120 ℃ of oil baths over to, the static insulation 36h that refluxes down.Behind the aged substance suction filtration (suction filtration is a kind of step with solid and fluid separation applications), with filter cake roasting direct 4h in 700 ℃ of Muffle furnaces.
The present invention is by adding the rate of addition of surfactant and control reaction raw materials, utilize the coating effect of surfactant under alkali condition, form electric double layer on the precipitation particles surface, the surface that has reduced particle can, help suppressing particle aggregation, improved the performance of target product.
Outstanding feature of the present invention has: the compound cerium zirconium sosoloid that 1) obtains presents single cube phase on XRD spectra, and the solid solution that forms single stable is described.2) used raw material are cheap and easy to get, and are simple to operate.3) compound cerium zirconium sosoloid oxygen storage capacity is strong.
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Description of drawings
Fig. 1 is that the compound cerium zirconium sosoloid of the present invention is at XRD spectra
Fig. 2 is that the compound cerium zirconium sosoloid of the present invention is 400 ℃ of following oxygen storage capacity test results.
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The specific embodiment:
Further set forth the present invention by specific embodiments of the invention given below.
The compound cerium zirconium sosoloid of a kind of high oxygen storage power, it is characterized in that mainly by cerium oxide, zirconia and
Auxiliary agent is composited, and adds the surfactant that can improve oxygen storage capacity in the preparation recombination process; The percentage by weight of its component constitutes, and with the composite oxides metering is cerium oxide 10 ~ 80%, zirconia 10 ~ 70%, auxiliary agent 10 ~ 20%; Described auxiliary agent is at least a in lanthana, neodymia, praseodymium oxide, the yittrium oxide, or wherein any two kinds, three kinds, the four kinds mixtures that mix to obtain with arbitrary proportion; Described surfactant is any one among polyethylene glycol PEG200, PEG2000, the PEG20000, or mix with arbitrary proportion for wherein two kinds, three kinds, or be PVAC polyvinylalcohol, or be PVA with polyethylene glycol PEG200, PEG2000, PEG20000 in any one or two kinds or three kinds mix with arbitrary proportion; The surfactant percentage by weight be in cerium oxide, zirconia and the auxiliary agent oxide aggregate 8 ~ 30%.PEG200, PEG2000, PEG20000 are the polymer of polyethylene glycol, and molecular weight is different; PVA is the chemical substance of high score subclass, polyvinyl alcohol.
Described cerium oxide percentage by weight can be 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% etc.; Described zirconia percentage by weight can be for 10%, 15%, 20%, 25%, 30%, 35%, 40%,, 45%, 50%, 55%, 60%, 65%, 70% etc., described auxiliary agent percentage by weight can be 10%, 12%, 14%, 15%, 16%, 17%, 18%, 19%, 20% etc.Described surfactant percentage by weight can be 10%, 11%, 12%, 14%, 15%, 16%18%, 20%, 22%, 24%, 25%, 26%, 28%, 30% etc. of oxide aggregate in cerium oxide, zirconia and the auxiliary agent.
Described cerium oxide percentage by weight is 45-60%, and described zirconia percentage by weight is 30-45%.
Said auxiliary agent is neodymia and praseodymium oxide.
Said auxiliary agent weight content is 8 ~ 14%.
The preparation method of the compound cerium zirconium sosoloid of the present invention is characterized in that cerium oxide, zirconia with metering
Be dissolved in respectively in the nitric acid with auxiliary agent, the solubility nitrate solution that makes mixes the back and is presoma, adds the surfactant of metering in presoma; Under fully stirring precursor solution is added in 50 ℃ ~ 70 ℃ ammonia spirits, it is precipitated fully; Then sediment is incubated the 24 ~ 48h that refluxes in 100 ~ 120 ℃; Behind the suction filtration, roasting direct 2.5-5h in 650-780 ℃ of roasters (Muffle furnace).
Compound cerium zirconium sosoloid of the present invention presents single cube phase at XRD spectra such as Fig. 1 on Fig. 1, the solid solution that forms single stable is described.
Embodiment 1
:The weight of compound cerium zirconium sosoloid consists of 30%CeO
2-60%ZrO
2-5%Nd
2O
3-5%Pr
6O
11CeO with aforementioned weight
2, ZrO
2, Nd
2O
3, Pr
6O
11Be dissolved in the nitric acid of suitable concn, obtain cerous nitrate, zirconium nitrate, neodymium nitrate, praseodymium nitrate solution, be mixed with mixed solution after mixing again; Add in mixed solution and account for oxide feed intake the polyethylene glycol PEG20000 and the PEG200 mixture of total amount 20%, wherein, the weight ratio of PEG20000 and PEG200 is 1:1, stirs.Get 150mL ammoniacal liquor+150mL distilled water in advance, mix the back and in 60 ℃ of water-baths, be incubated.Under agitation the speed with 10-20mL/min joins (best adding speed is 15mL/min) in the ammoniacal liquor with nitrate mixed solution, and it is precipitated fully, and the control endpoint pH is between 9.2-10.8, and best pH value is 10, and precipitation reaction finishes.This moment, solution presented purplish greyish white solid-liquid mixture.Change sediment over to 100 ~ 120 ℃ of oil baths together with mother liquor, the static backflow down is incubated a period of time, as 30-45h.Behind the aged substance suction filtration, it is 700 ℃) with filter cake roasting direct 2.5-5h(optimum temperature in 650-780 ℃ of Muffle furnaces; Obtain dun cerium zirconium sosoloid at last.
Embodiment 2
:The weight of compound cerium zirconium sosoloid consists of 45%CeO
2-45%ZrO
2-5%Nd
2O
3-5%Pr
6O
11Surplus with embodiment 1.
Embodiment 3
:The weight of compound cerium zirconium sosoloid consists of 55%CeO
2-25%ZrO
2-5%Nd
2O
3-5%Pr
6O
11Surplus with embodiment 1.
The comparative example 1
:The weight of compound cerium zirconium sosoloid consists of 30%CeO
2-60%ZrO
2-5%Nd
2O
3-5%Pr
6O
11Cerous nitrate, zirconium nitrate, neodymium nitrate, the praseodymium nitrate of metering are mixed with mixed solution, stir.Get 150mL ammoniacal liquor+150mL distilled water in advance, mix the back and in 60 ℃ of water-baths, be incubated.Under agitation the speed with 15mL/min joins nitrate mixed solution in the ammoniacal liquor, and it is precipitated fully, control terminal point pH 10.0, and precipitation reaction finishes.This moment, solution presented purplish greyish white solid-liquid mixture.Change sediment over to 100 ~ 120 ℃ of oil baths together with mother liquor, the static insulation 36h that refluxes down.Behind the aged substance suction filtration, with filter cake roasting direct 4h in 700 ℃ of Muffle furnaces.Obtain dun cerium zirconium sosoloid at last.
The comparative example 2
:The weight of compound cerium zirconium sosoloid consists of 45%CeO
2-45%ZrO
2-5%Nd
2O
3-5%Pr
6O
11Cerous nitrate, zirconium nitrate, neodymium nitrate, the praseodymium nitrate of metering are mixed with mixed solution, stir.Get 150mL ammoniacal liquor+150mL distilled water in advance, mix the back and in 60 ℃ of water-baths, be incubated.Under agitation the speed with 15mL/min joins nitrate mixed solution in the ammoniacal liquor, and it is precipitated fully, control terminal point pH 10.0, and precipitation reaction finishes.This moment, solution presented purplish greyish white solid-liquid mixture.Change sediment over to 100 ~ 120 ℃ of oil baths together with mother liquor, the static insulation 36h that refluxes down.Behind the aged substance suction filtration, with filter cake roasting direct 4h in 700 ℃ of Muffle furnaces.Obtain dun cerium zirconium sosoloid at last.
The comparative example 3
:The weight of compound cerium zirconium sosoloid consists of 60%CeO
2-30%ZrO
2-5%Nd
2O
3-5%Pr
6O
11Cerous nitrate, zirconium nitrate, neodymium nitrate, the praseodymium nitrate of metering are mixed with mixed solution, stir.Get 150mL ammoniacal liquor+150mL distilled water in advance, mix the back and in 60 ℃ of water-baths, be incubated.Under agitation the speed with 15mL/min joins nitrate mixed solution in the ammoniacal liquor, and it is precipitated fully, control terminal point pH 10.0, and precipitation reaction finishes.This moment, solution presented purplish greyish white solid-liquid mixture.Change sediment over to 100 ~ 120 ℃ of oil baths together with mother liquor, the static insulation 36h that refluxes down.Behind the aged substance suction filtration, with filter cake roasting direct 4h in 700 ℃ of Muffle furnaces.Obtain dun cerium zirconium sosoloid at last.
Cerium zirconium sosoloid among embodiment 1 ~ 3 and the comparative example 1 ~ 3 is carried out 400 ℃ of following oxygen storage capacity tests (in the test of Industrial Catalysis research institute of East China University of Science), the results are shown in accompanying drawing 2.Through the solid solution of surfactant activation processing, its oxygen storage capacity obviously is better than the solid solution that does not pass through the surfactant activation processing, and its oxygen storage capacity is greatly enhanced.
Claims (9)
1. compound cerium zirconium sosoloid of high oxygen storage power, it is characterized in that mainly by cerium oxide,
Zirconia and auxiliary agent are composited, and add the surfactant that can improve oxygen storage capacity in the preparation recombination process; The percentage by weight of its component constitutes, and with the composite oxides metering is cerium oxide 10 ~ 80%, zirconia 10 ~ 70%, auxiliary agent 10 ~ 20%; Described auxiliary agent is at least a in lanthana, neodymia, praseodymium oxide, the yittrium oxide, or wherein any two kinds, three kinds, four kinds are mixed with arbitrary proportion;
Described surfactant is any one among polyethylene glycol PEG200, PEG2000, the PEG20000, or mix with arbitrary proportion for wherein two kinds, three kinds, or be PVAC polyvinylalcohol, or be PVA with polyethylene glycol PEG200, PEG2000, PEG20000 in any one or two kinds or three kinds mix with arbitrary proportion; Percentage by weight be in cerium oxide, zirconia and the auxiliary agent oxide aggregate 10 ~ 30%.
2. compound cerium zirconium sosoloid according to claim 1 is characterized in that described cerium oxide percentage by weight is 45-60%, and described zirconia percentage by weight is 30-45%.
3. compound cerium zirconium sosoloid according to claim 1 is characterized in that said auxiliary agent is neodymia and praseodymium oxide.
4. compound cerium zirconium sosoloid according to claim 1 is characterized in that said auxiliary agent weight content is 8 ~ 14%.
5. the preparation method of the described compound cerium zirconium sosoloid of claim 1 to 4, it is characterized in that with
Cerium oxide, zirconia and the auxiliary agent of metering are dissolved in respectively in the nitric acid, and the solubility nitrate solution that makes mixes the back and is presoma, adds the surfactant of metering in presoma; Be added dropwise in 50 ℃ ~ 70 ℃ ammonia spirits to precursor solution under fully stirring, it is precipitated fully; Then sediment is incubated the 24 ~ 48h that refluxes in 100 ~ 120 ℃; Behind the suction filtration, roasting direct 2.5-5h in 650-780 ℃ of Muffle furnaces.
6. according to the preparation method of claim 1 and the described compound cerium zirconium sosoloid of claim 5, it is characterized in that said surfactant is any one among polyethylene glycol PEG200, PEG2000, the PEG20000, or mix with arbitrary proportion for wherein two kinds, three kinds, or be PVAC polyvinylalcohol, or be PVA with polyethylene glycol PEG200, PEG2000, PEG20000 in any one or two kinds or three kinds mix with arbitrary proportion; Consumption be in the precursor solution oxide aggregate 10 ~ 30%.
7. according to the preparation method of the described compound cerium zirconium sosoloid of claim 6, it is characterized in that said surfactant is the mixture of polyethylene glycol PEG200+PEG20000, addition be in the precursor solution oxide aggregate 20%.
8. according to the preparation method of the described compound cerium zirconium sosoloid of claim 5, it is characterized in that the speed that is added dropwise to of precursor solution adding ammoniacal liquor is 10-20mL/min.
9. the preparation method of described compound cerium zirconium sosoloid according to Claim 8, the speed that is added dropwise to that it is characterized in that precursor solution is 15mL/min.
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| CN102580718A (en) * | 2012-02-02 | 2012-07-18 | 福州大学 | Cerium-zirconium composite material, preparation method thereof and application thereof |
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