CN101637721A - Porous yttrium-cerium-zirconium solid solution and preparation method thereof - Google Patents
Porous yttrium-cerium-zirconium solid solution and preparation method thereof Download PDFInfo
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- CN101637721A CN101637721A CN200910056615A CN200910056615A CN101637721A CN 101637721 A CN101637721 A CN 101637721A CN 200910056615 A CN200910056615 A CN 200910056615A CN 200910056615 A CN200910056615 A CN 200910056615A CN 101637721 A CN101637721 A CN 101637721A
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Abstract
The invention provides porous yttrium-cerium-zirconium solid solution and a preparation method thereof; the structural general formula of the porous yttrium-cerium-zirconium solid solution is as follows: Ce<x>Zr<0.9-x>Y<0.1>O2. The preparation method comprises the following steps: adding protective agent, mixed metal salt solution and activity polystyrene microballoon emulsion into precipitator, reacting for 1-2 hours in the normal temperature, ageing for 1-3 hours in the temperature of 80-100 DEG C, collecting precipitate, washing, dried for 1-5 hours in the temperature of 80-150 DEG C, roasting dry products for 1-6 h in the temperature of 300-1000 DEG C to obtain the porous yttrium-cerium-zirconium solid solution. The invention has higher specific surface area, heat stability, excellentchemical activity, high oxygen storage capability and high temperature heat stability, and has wide application in automobile exhaust cleaning catalyst, catalytic combustion catalyzer and other catalyzers.
Description
Technical field
The present invention relates to a kind of porous yttrium-cerium-zirconium solid solution and preparation method thereof, relate in particular to a kind of porous yttrium-cerium-zirconium solid solution that is used for cleaning catalyst for tail gases of automobiles and is used as other catalysis material.
Background technology
Harmful components in the automobile engine to exhaust mainly contain CO, HC and NO
x, not only the severe contamination atmosphere, worsen environment, and threaten directly that people's is healthy.The catalytic cleaning of car tail gas technology is to administer one of the most effective, reliable technique of auto-pollution thing now, and three-way catalyst is can be with CO, HC, NO
xThe purifying vehicle exhaust catalyst of removing simultaneously.Present particular importance and that play a crucial role is cerium oxide (CeO in such catalyst
2) and zirconia (ZrO
2) two kinds of components.Cerium oxide is owing to exist Ce
3+And Ce
4+The redox transfer capability and in cleaning catalyst for tail gases of automobiles, be widely used.With ZrO
2Add CeO to
2In, can form CeO
2-ZrO
2Solid solution and improve CeO
2The body phase behaviour, be beneficial to the migration and the diffusion of body phase oxygen atom, body phase reaction process is become vivaciously, can improve CeO
2Oxygen storage capacity.The rare earth zirconium solid solution hydrogen-storing material of Heat stability is good is a kind of catalyst aid of good purifying vehicle exhaust, because the adding of rare earth zirconium solid solution hydrogen-storing material, not only reduced the consumption of noble metal in the catalyst, and improved catalytic activity, oxygen storage capacity, catalytic selectivity, enlarged the air-fuel ratio operation window.In addition because catalytic reaction mainly occurs in catalyst surface, so the high-specific surface area of hydrogen-storing material, good high-temperature heat endurance are the prerequisites of high catalytic capability.The preparation of bigger serface hydrogen-storing material considers to exist certain limitation from granularity itself merely, and the way that increases specific area is material is made loose structure.When the aperture was big, the specific area of material was not very big; And the aperture hour, although the specific area of material increases, but owing to easily subside at the medium and small pore volume of roasting process, the high-temperature stability of material has decline to a certain degree again, therefore there is the pore structure of a suitable size, makes material when having big specific area, have good high-temperature stability again.
Patent CN1369460A discloses a kind of preparation method of Ce-Zr based composite oxide.With nitrate is raw material, and carbonic hydroammonium is precipitating reagent, through processes such as precipitation reaction, drying, roastings, prepares a kind ofly based on cerium oxide and zirconic Ce-Zr based composite oxide, and behind 500 ℃ of roasting 2h, specific area is 40～50m
2G
-1The specific area of this method gained Ce-Zr based composite oxide is less.
Patent CN101112683A discloses a kind of meso-hole structure cerium zirconium aluminum composite oxides sosoloid and preparation method thereof.With nitrate is raw material, with NaOH is precipitating reagent, with hexadecyltrimethylammonium chloride as template, through processes such as precipitation reaction, drying, roastings, prepare a kind of meso-hole structure cerium zirconium aluminum composite oxides sosoloid, the specific area of sample is bigger after 450 ℃ of roastings, but average pore size only is 2.5～3.4nm, aperture generation sintering behind the high temperature ageing, the specific area after wearing out is less.
Summary of the invention
The purpose of this invention is to provide a kind of porous yttrium-cerium-zirconium solid solution and preparation method thereof, to overcome the above-mentioned defective that prior art exists.
The general structure of the said porous yttrium-cerium-zirconium solid solution of the present invention is:
Ce
xZr
0.9-xY
0.1O
2
Wherein: x=0.1～0.8 is preferably 0.2～0.7.
Described porous yttrium-cerium-zirconium solid solution, 400～500 ℃ of roasting 2～3h, specific area is 100～150m
2G
-1, the aperture is 7～10nm; 900～1000 ℃ of aging 4～5h, specific area is 35～60m
2G
-1
The preparation method of porous yttrium-cerium-zirconium solid solution of the present invention comprises the steps:
Precipitating reagent is added protective agent, mixed salt solution and active polystyrene microballoon emulsion; reacted at normal temperatures 1～2 hour; then at 80～100 ℃ of ageing 1～3h; collecting precipitation thing, washing; again in 80～150 ℃ of down dry 1～5h; desciccate obtains said porous yttrium-cerium-zirconium solid solution at 300～1000 ℃ of roasting 1～6h.
Described protective agent is selected from the polyethylene glycol of molecular weight 2000～6000;
Described mixed salt solution is the aqueous solution that contains cerium salt, zirconates and yttrium salt, wherein:
Described cerium salt is selected from cerous nitrate or cerous chlorate, and in the aqueous solution, concentration is 0.1～1mol/L;
Described zirconates is selected from zirconium nitrate, zirconyl nitrate or basic zirconium chloride, and in the aqueous solution, concentration is 0.1～1mol/L;
Described yttrium salt is selected from yttrium nitrate or yttrium chloride, and in the aqueous solution, concentration is 0.1～1mol/L;
It is that 20～35% ammoniacal liquor, weight concentration are that 25～45% sodium hydrate aqueous solution, weight concentration are that 25～35% potassium hydroxide aqueous solution or weight concentration are one or both in 10～25% the ammonium carbonate solution that described precipitating reagent is selected from weight concentration, and it is 9～10 that the addition of precipitating reagent makes the pH of reaction end;
The volume ratio of active polystyrene microballoon emulsion and mixed salt solution is 0.1: 1～1: 1;
The mass ratio of protective agent and active polystyrene microballoon is 0.1: 1～1: 1;
In the described active polystyrene microballoon emulsion, the concentration of active polystyrene microballoon is 0.2～0.25gmL
-1
Described active polystyrene microballoon emulsion can adopt CN1793187A patent documentation reported method to be prepared, and preferred, the preparation method comprises the steps:
Under nitrogen protection, 65～70 ℃ of stirring reaction 40～60min add silane coupler again with styrene monomer, initator, emulsifying agent, buffer and water, behind reaction 7～9h, obtain active polystyrene microballoon emulsion;
Described initator is selected from ammonium persulfate, potassium peroxydisulfate or dibenzoyl peroxide;
Described emulsifying agent is selected from one or both in dodecyl sodium sulfate, lauryl sodium sulfate or the neopelex;
Described buffer is selected from one or both in saleratus or the sodium acid carbonate;
Described silane coupler is selected from γ-(methacryloxypropyl) propyl trimethoxy silicane, γ-neon propyl group front three nitrogen base silane, γ-(2, the 3-glycidoxy) propyl trimethoxy silicane or β-(3,4-epoxy cyclohexyl) ethyl trimethoxy silane;
Monomer styrene: initator: emulsifying agent: buffer: silane coupler=200: 4～7: 0～1: 0～9: 5～45, mass ratio;
The present invention is template with the polystyrene microsphere, adopts liquid-phase coprecipitation to prepare porous yttrium-cerium-zirconium solid solution.This solid solution crystallization degree height, specific area are big, and preparation technology is simple, the industrialization processing ease.
The porous yttrium-cerium-zirconium solid solution that makes with the inventive method is the uniform solid solution class of an a kind of single cubic phase structure multicomponent composite oxide, has higher specific surface area and heat endurance, 400～500 ℃ of roasting 2～3h, and specific area is 100～150m
2G
-1, the aperture is 7～10nm, specific area still can reach 35～60m behind 900 ℃ of roasting 4h
2G
-1Porous yttrium-cerium-zirconium solid solution of the present invention has excellent in chemical activity, high oxygen storage capacity and high high-temp stability, in cleaning catalyst for tail gases of automobiles, catalyst for catalytic combustion and other catalyst, has a wide range of applications.
Description of drawings
Fig. 1 is the XRD spectra of embodiment 1.
Fig. 2 is the XRD spectra of embodiment 2.
Fig. 3 is the XRD spectra of embodiment 3.
Fig. 4 is the XRD spectra of embodiment 3.
Fig. 5 is the XRD spectra of embodiment 4.
Fig. 6 is the XRD spectra of embodiment 5.
Fig. 7 is the XRD spectra of embodiment 6.
Fig. 8 is the XRD spectra of embodiment 7.
The specific embodiment
Specific area of the present invention and aperture all adopt the Tristar 3000 type specific area pore analysis instrument of U.S. Merck ﹠ Co., Inc to measure.
Solid solution of the present invention exists with pure solid solution form, can change the full-automatic diffraction analysis instrument of target by Rigaku D/max-2550VB/PC type and characterize.
The said oxygen storage capacity of the present invention is the buffer capacity of solid solution to oxygen, estimates with its ability that stores oxygen and discharge oxygen in oxidation environment in reducing environment.Solid solution is containing 10%H earlier
2Hydrogen helium gas mixture body in temperature programmed reduction, be cooled to 400 ℃ then and carry out O
2The thermal conductivity detector (TCD) analytical gas is used in the pulse titration.Quantity by the oxygen that consumes can be measured oxygen storage capacity.The characteristic value of oxygen storage capacity is expressed with the μ mol number of the solid solution product institute oxygen consumed that every gram is introduced.
Embodiment 1
In four-hole boiling flask, add 0.4g ammonium persulfate and 0.8g NaHCO
3And 120mL distilled water; after stirring 10min; add the 20mL styrene monomer; and logical nitrogen is protected in four-hole boiling flask, is warming up to 70 ℃ of afterreaction 1h, adds 4g γ-(methacryloxypropyl) propyl trimethoxy silicane again; continue reaction 9h; cooling, static obtained white emulsion after question response was finished, and is stand-by.
Get above-mentioned white emulsion, add water and be made into active polystyrene microballoon 0.2gmL
-1Active polystyrene emulsion 200mL, pour in the there-necked flask that condenser pipe and agitator are housed, mixing speed is 100rpm, adds deionized water 1000mL and 18g Macrogol 4000.
With 90mL concentration is 0.5molL
-1The cerous chlorate aqueous solution, 45mL concentration be 1molL
-1The dichlorooxazirconium aqueous solution and 100mL concentration be 0.1molL
-1The yttrium chloride aqueous solution join in the there-necked flask, mixing speed is brought up to 400rpm, add weight concentration then and be 35% ammoniacal liquor, the pH of control reaction end is 9, reacts at normal temperatures 1 hour, product is behind 80 ℃ of ageing 3h, filter, wash, and, place 500 ℃ of roasting 2h of Muffle furnace then in 100 ℃ of following dry 1h, promptly get porous yttrium-cerium-zirconium solid solution, specific area is 128m
2G
-1, average pore size is 8.1nm, oxygen storage capacity is 412 μ molg
-1, its XRD spectra is seen Fig. 1.Get about 5g porous yttrium-cerium-zirconium solid solution and place that specific area is 45m behind 900 ℃ of following roasting 4h of Muffle furnace
2G
-1, oxygen storage capacity is 298 μ molg
-1
In four-hole boiling flask, add 0.4g ammonium persulfate and 0.1g neopelex and 120mL distilled water; after stirring 10min; add the 20mL styrene monomer; and logical nitrogen is protected in four-hole boiling flask, is warming up to 70 ℃ of afterreaction 1h, adds 4g γ-(methacryloxypropyl) propyl trimethoxy silicane; continue reaction 9h; cooling, static obtained white emulsion after question response was finished, and is stand-by.
Get above-mentioned white emulsion, regulate being made into active polystyrene microballoon 0.23gmL
-1Active polystyrene emulsion 200mL, pour in the there-necked flask that condenser pipe and agitator are housed, mixing speed is 100rpm, adds deionized water 1000mL and 20g Macrogol 2000.
With 120mL concentration is 0.5molL
-1The cerous nitrate aqueous solution, 60mL concentration be 0.5molL
-1The zirconyl nitrate aqueous solution and 50mL concentration be 0.2molL
-1The yttrium chloride aqueous solution join in the there-necked flask, mixing speed is brought up to 400rpm, add weight concentration then and be 45% sodium hydroxide solution, control reaction end pH reacted 1.5 hours at normal temperatures 10, product is behind 90 ℃ of ageing 3h, filter, wash, and, place 500 ℃ of roasting 2h of Muffle furnace then in 100 ℃ of following dry 1h, promptly get porous yttrium-cerium-zirconium solid solution, specific area is 116m
2G
-1, average pore size is 8.7nm, oxygen storage capacity is 372 μ molg
-1Get about 5g porous yttrium-cerium-zirconium solid solution and place that specific area is 39m behind 900 ℃ of following roasting 4h of Muffle furnace
2G
-1, oxygen storage capacity is 229 μ molg
-1, its XRD spectra is seen Fig. 2.
Embodiment 3
In four-hole boiling flask, add 0.4g ammonium persulfate and 0.8g KHCO
3And 120mL distilled water; after stirring 10min; add the 20mL styrene monomer again; and logical nitrogen is protected in four-hole boiling flask, is warming up to 70 ℃ of afterreaction 1h, slowly adds 4g γ-(methacryloxypropyl) propyl trimethoxy silicane again; continue reaction 9h; cooling, static obtained white emulsion after question response was finished, and is stand-by.
Get above-mentioned white emulsion, add water and be made into active polystyrene microballoon 0.25gmL
-1Active polystyrene emulsion 200mL, pour in the there-necked flask that condenser pipe and agitator are housed, mixing speed is 100rpm, adds deionized water 1000mL and 20g Macrogol 4000.
With 50mL concentration is 1molL
-1The cerous nitrate aqueous solution, 40mL concentration be 1molL
-1The zirconyl nitrate aqueous solution and 25mL concentration be 0.4molL
-1The yttrium chloride aqueous solution join in the there-necked flask, mixing speed is brought up to 400rpm, add weight concentration then and be 25% ammoniacal liquor, control reaction end pH reacted 1 hour at normal temperatures 9, product is behind 90 ℃ of ageing 3h, filter, wash, and, place 500 ℃ of roasting 2h of Muffle furnace then in 100 ℃ of following dry 1h, promptly get porous yttrium-cerium-zirconium solid solution, specific area is 121m
2G
-1, average pore size is 8.2nm, oxygen storage capacity is 405 μ molg
-1, its XRD spectra is seen Fig. 3.Get about 5g porous yttrium-cerium-zirconium solid solution and place that specific area is 42m behind 900 ℃ of following roasting 4h of Muffle furnace
2G
-1, oxygen storage capacity is 271 μ molg
-1, its XRD spectra is seen Fig. 4.
Embodiment 4
In four-hole boiling flask, add 0.4g ammonium persulfate and 0.8g NaHCO
3And 120mL distilled water; after stirring 10min; add the 20mL styrene monomer; and logical nitrogen is protected in four-hole boiling flask, is warming up to 70 ℃ of afterreaction 1h, adds 4g γ-(methacryloxypropyl) propyl trimethoxy silicane again; continue reaction 9h; cooling, static obtained white emulsion after question response was finished, and is stand-by.
Get above-mentioned white emulsion, regulate being made into active polystyrene microballoon 0.21gmL
-1Active polystyrene emulsion 200mL, pour in the there-necked flask that condenser pipe and agitator are housed, mixing speed is 100rpm, adds deionized water 1000mL and 20g Macrogol 2000.
With 200mL concentration is 0.2molL
-1The cerous nitrate aqueous solution, 125mL concentration be 0.4molL
-1The zirconyl nitrate aqueous solution and 10mL concentration be 1molL
-1The yttrium chloride aqueous solution join in the there-necked flask, mixing speed is brought up to 400rpm, add weight concentration then and be 10% ammonium carbonate solution, control reaction end pH reacted 2 hours at normal temperatures 10, product is behind 80 ℃ of ageing 3h, filter, wash, and, place 500 ℃ of roasting 2h of Muffle furnace then in 100 ℃ of following dry 1h, promptly get porous yttrium-cerium-zirconium solid solution, specific area is 141m
2G
-1, average pore size is 7.5nm, oxygen storage capacity is 363 μ molg
-1, its XRD spectra is seen Fig. 5.Get about 5g porous yttrium-cerium-zirconium solid solution and place that specific area is 54m behind 900 ℃ of following roasting 4h of Muffle furnace
2G
-1, oxygen storage capacity is 238 μ molg
-1
Embodiment 5
Prepare the active polystyrene emulsion according to embodiment 4 identical methods.
With 30mL concentration is 1molL
-1The cerous nitrate aqueous solution, 75mL concentration be 0.8molL
-1The zirconyl nitrate aqueous solution and 20mL concentration be 0.5molL
-1The yttrium chloride aqueous solution join in the there-necked flask, mixing speed is brought up to 400rpm, drips 6molL then
-1Ammonium carbonate and the mixed aqueous solution of ammoniacal liquor, reaction end pH is 10 in control, reacts at normal temperatures 1 hour, product filters, washes behind 90 ℃ of ageing 3h, and in 100 ℃ of following dry 1h, promptly get porous yttrium-cerium-zirconium solid solution after placing 500 ℃ of roasting 2h of Muffle furnace then, specific area is 147m
2G
-1, average pore size is 7.3nm, oxygen storage capacity is 389 μ molg
-1, its XRD spectra is seen Fig. 6.Get about 5g porous yttrium-cerium-zirconium solid solution and place that specific area is 59m behind 900 ℃ of following roasting 4h of Muffle furnace
2G
-1, oxygen storage capacity is 267 μ molg
-1
Embodiment 6
Prepare the active polystyrene emulsion according to embodiment 4 identical methods.
With 40mL concentration is 0.5molL
-1The cerous nitrate aqueous solution, 100mL concentration be 0.7molL
-1The zirconyl nitrate aqueous solution and 10mL concentration be 1molL
-1The yttrium chloride aqueous solution join in the there-necked flask, mixing speed is brought up to 400rpm, add weight concentration then and be 35% ammoniacal liquor, control reaction end pH reacted 1 hour at normal temperatures 9, and product is behind 90 ℃ of ageing 2h, filter, wash, and, promptly getting porous yttrium-cerium-zirconium solid solution after placing 500 ℃ of roasting 2h of Muffle furnace then in 100 ℃ of following dry 1h, specific area is 134m
2G
-1, average pore size is 7.8nm, oxygen storage capacity is 324 μ molg
-1, its XRD spectra is seen Fig. 7.Get about 5g porous yttrium-cerium-zirconium solid solution and place that specific area is 49m behind 900 ℃ of following roasting 4h of Muffle furnace
2G
-1, oxygen storage capacity is 193 μ molg
-1
Embodiment 7
Prepare the active polystyrene emulsion according to embodiment 4 identical methods.
With 100mL concentration is 0.7molL
-1The cerous nitrate aqueous solution, 20mL concentration be 1molL
-1The zirconyl nitrate aqueous solution and 50mL concentration be 0.2molL
-1The yttrium chloride aqueous solution join in the there-necked flask, mixing speed is brought up to 400rpm, drips 6molL then
-1Ammonium carbonate and the mixed aqueous solution of ammoniacal liquor, reaction end pH is 10 in control, reacts at normal temperatures 1 hour, product filters, washes behind 90 ℃ of ageing 3h, and in 100 ℃ of following dry 1h, place 500 ℃ of roasting 2h of Muffle furnace then, promptly get porous yttrium-cerium-zirconium solid solution, specific area is 116m
2G
-1, average pore size is 8.5nm, oxygen storage capacity is 353 μ molg
-1, its XRD spectra is seen Fig. 8.Get about 5g porous yttrium-cerium-zirconium solid solution and place that specific area is 39m behind 900 ℃ of following roasting 4h of Muffle furnace
2G
-1, oxygen storage capacity is 214 μ molg
-1
Claims (9)
1. porous yttrium-cerium-zirconium solid solution is characterized in that, general structure is:
Ce
xZr
0.9-xY
0.1O
2
Wherein: x=0.1～0.8.
2. porous yttrium-cerium-zirconium solid solution according to claim 1 is characterized in that, x=0.2～0.7.
3. porous yttrium-cerium-zirconium solid solution according to claim 1 is characterized in that, described porous yttrium-cerium-zirconium solid solution, and 400～500 ℃ of roasting 2～3h, specific area is 100～150m
2G
-1, the aperture is 7～10nm;
900～1000 ℃ of aging 4～5h, specific area is 35～60m
2G
-1
4. the preparation method of porous yttrium-cerium-zirconium solid solution according to claim 1; it is characterized in that; comprise the steps: precipitating reagent is added protective agent, mixed salt solution and active polystyrene microballoon emulsion; reacted at normal temperatures 1～2 hour; at 80～100 ℃ of ageing 1～3h, collecting precipitation thing, washing are again in 80～150 ℃ of down dry 1～5h then; desciccate obtains said porous yttrium-cerium-zirconium solid solution at 300～1000 ℃ of roasting 1～6h.
5. method according to claim 4 is characterized in that described protective agent is selected from the polyethylene glycol of molecular weight 2000～6000.
6. method according to claim 4 is characterized in that, described mixed salt solution is the aqueous solution that contains cerium salt, zirconates and yttrium salt, and wherein: described cerium salt is selected from cerous nitrate or cerous chlorate, and in the aqueous solution, concentration is 0.1～1mol/L;
Described zirconates is selected from zirconium nitrate, zirconyl nitrate or basic zirconium chloride, and in the aqueous solution, concentration is 0.1～1mol/L;
Described yttrium salt is selected from yttrium nitrate or yttrium chloride, and in the aqueous solution, concentration is 0.1～1mol/L.
7. method according to claim 4, it is characterized in that, it is that 20～35% ammoniacal liquor, weight concentration are that 25～45% sodium hydrate aqueous solution, weight concentration are that 25～35% potassium hydroxide aqueous solution or weight concentration are one or both in 10～25% the ammonium carbonate solution that described precipitating reagent is selected from weight concentration, and it is 9～10 that the addition of precipitating reagent makes the pH of reaction end.
8. method according to claim 4 is characterized in that, the volume ratio of active polystyrene microballoon emulsion and mixed salt solution is 0.1: 1～1: 1;
The mass ratio of protective agent and active polystyrene microballoon is 0.1: 1～1: 1;
In the described active polystyrene microballoon emulsion, the concentration of active polystyrene microballoon is 0.2～0.25gmL
-1
9. method according to claim 4 is characterized in that, the preparation method of described active polystyrene microballoon emulsion comprises the steps:
Under nitrogen protection, 65～70 ℃ of stirring reaction 40～60min add silane coupler again with styrene monomer, initator, emulsifying agent, buffer and water, behind reaction 7～9h, obtain active polystyrene microballoon emulsion;
Described initator is selected from ammonium persulfate, potassium peroxydisulfate or dibenzoyl peroxide;
Described emulsifying agent is selected from one or both in dodecyl sodium sulfate, lauryl sodium sulfate or the neopelex;
Described buffer is selected from one or both in saleratus or the sodium acid carbonate;
Described silane coupler is selected from γ-(methacryloxypropyl) propyl trimethoxy silicane, γ-neon propyl group front three nitrogen base silane, γ-(2, the 3-glycidoxy) propyl trimethoxy silicane or β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane;
Monomer styrene: initator: emulsifying agent: buffer: silane coupler=200: 4～7: 0～1: 0～9: 5～45, mass ratio.
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