WO2011108457A1 - 酸化セリウム-酸化ジルコニウム系複合酸化物及びその製造方法 - Google Patents
酸化セリウム-酸化ジルコニウム系複合酸化物及びその製造方法 Download PDFInfo
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
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- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
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Definitions
- the present invention relates to a cerium oxide-zirconium oxide composite oxide and a method for producing the same.
- Cerium oxide has a small redox potential of Ce 4+ and Ce 3+ of about 1.6 V, and the reaction of the following formula proceeds reversibly, so it has an oxygen storage and release capability (hereinafter referred to as OSC). It is used as a co-catalyst or catalyst carrier for a three-way catalyst for automobiles.
- Patent Document 1 states that “a composite oxide containing cerium and zirconium, (1) the oxygen release start temperature is 380 ° C. or less, and (2) the oxygen release amount is 485 ⁇ mol / g or more. (3) A cerium-zirconium based composite oxide characterized in that the amount of released oxygen at 400 ° C. is 15 ⁇ mol / g or more. ”
- This composite oxide containing cerium and zirconium is obtained by melting a raw material mixture obtained by mixing a cerium raw material containing cerium oxide and a zirconium raw material containing zirconium oxide at a predetermined ratio at a temperature equal to or higher than the melting point. Then, the obtained melt is cooled to form an ingot, and then the ingot is pulverized into a powder. If desired, the distortion in the powder crystal is removed under heating, and then further finely pulverized. Is obtained. Therefore, unlike a complex oxide containing cerium and zirconium obtained by a normal wet method, it is obtained by a melting method (dry method), and thus has the above unique characteristics.
- crystallite size means that the number of atoms in the structure (that is, internal energy) is larger than the number of atoms on the surface (that is, surface energy), and the surface becomes inactive when considered in particle units. To do. In other words, oxygen in the bulk is easy to move in terms of energy, but oxygen on the surface is difficult to move.
- this composite metal oxide has a feature of excellent dispersibility of platinum, there is a problem that OSC at a low temperature is small.
- Patent Document 3 provides “a sol containing at least colloidal particles of ceria-zirconia solid solution having different isoelectric points and colloidal particles of a second metal oxide, and adjusting the pH of the sol to the second value.
- the colloidal particles of the ceria-zirconia solid solution are agglomerated closer to the isoelectric point of the colloidal particles of the ceria-zirconia solid solution than the isoelectric point of the colloidal particles of the metal oxide.
- the second metal oxide is disposed around the aggregated ceria-zirconia solid solution colloidal particles closer to the isoelectric point of the colloidal particles of the second metal oxide than the isoelectric point of the colloidal particles of zirconia solid solution.
- a center rich in ceria-zirconia solid solution comprising agglomerating the colloidal particles of the material and drying and calcining the resulting agglomerates
- Method Metal oxide particles having a sheath portion comprising a relatively large amount of second metal oxides is described.
- this production method has problems such as the use of colloidal particles of ceria-zirconia solid solution and colloidal particles of the second metal oxide, and other problems such as complicated operation and low OSC of the metal oxide particles at low temperatures. .
- the present invention has been made in view of the above problems, and its object is to provide a cerium oxide-zirconium oxide composite oxide having a large OSC at a low temperature and an appropriate OSC, and a simple production thereof. It is to provide a method.
- cerium oxide-zirconium oxide composite oxide provides the following cerium oxide-zirconium oxide composite oxide and a method for producing the same.
- a cerium oxide-zirconium oxide composite oxide characterized by mixing a cerium-zirconium composite oxide derived from a melting method and (2) a cerium dioxide derived from a wet method.
- 2. The cerium oxide-zirconium oxide composite oxide according to 1 above, wherein the crystallite diameter of the cerium-zirconium composite oxide derived from the melting method is 50 nm or more and the crystallite diameter of cerium dioxide derived from the wet process is less than 50 nm. 3. 3.
- the cerium oxide-zirconium oxide composite oxide according to any one of 1 to 3, wherein (1) :( 2) (weight ratio) 20 to 99: 1 to 80. 5.
- the cerium oxide-zirconium oxide composite oxide according to any one of 1 to 4 wherein the cerium-zirconium composite oxide derived from the melting method contains one or more rare earth oxides (excluding cerium oxide). 6). 6.
- a method for producing a cerium oxide-zirconium oxide-based composite oxide comprising dispersing a cerium-zirconium composite oxide derived from a melting method in a cerium-containing solution, neutralizing, and then heat-treating. 8).
- 9. The method for producing a cerium oxide-zirconium oxide composite oxide as described in 7 or 8 above, wherein the crystallite diameter of the cerium-zirconium composite oxide derived from the melting method is 50 nm or more. 10. 10.
- cerium oxide-zirconium oxide composite oxide having a large OSC at a low temperature and an appropriate OSC, and a simple production method thereof.
- the cerium oxide-zirconium oxide composite oxide of the present invention can be suitably used in the field as a three-way catalyst promoter for an automobile, an OSC material, a catalyst carrier, or the like.
- FIG. 3 is a diagram showing an X-ray diffraction result of the oxide powder obtained in Example 1.
- FIG. 4 is a view showing an X-ray diffraction result of the oxide powder obtained in Example 2. It is a figure which shows the measurement result of OSC at the time of changing the weight ratio of (1) the cerium-zirconium composite oxide derived from the melting method and (2) the cerium dioxide derived from the wet method.
- FIG. 6 is a diagram showing the H 2 -TPR measurement results of the oxide powders obtained in Example 2, Comparative Example 3 and Comparative Example 4.
- the cerium oxide-zirconium oxide composite oxide of the present invention and the production method thereof will be described in detail.
- the zirconium oxide (zirconia) as used in the field of this invention is a general thing, and contains the impurity metal compound of 10 weight% or less including hafnia.
- cerium Oxide-Zirconium Oxide Composite Oxide includes a mixture of “(1) a cerium-zirconium composite oxide derived from a melting method and (2) cerium dioxide derived from a wet method. It is characterized by that.
- the crystallite size of the “cerium-zirconium composite oxide derived from the melting method” is preferably 50 nm or more, more preferably 80 nm or more, and particularly preferably 100 nm or more.
- the crystallite size of the “cerium dioxide derived from the wet method” is Preferably it is less than 50 nm, More preferably, it is 30 nm or less, Most preferably, it is 20 nm or less.
- the upper limit of the crystallite diameter of the “cerium-zirconium composite oxide derived from the melting method” is not particularly limited, but is about 300 nm.
- the lower limit of the crystallite diameter of “cerium dioxide derived from a wet process” is not particularly limited, but is about 1 nm.
- the “cerium-zirconium composite oxide derived from the melting method” is not particularly limited, but refers to those produced by the following method and equivalents thereof.
- a raw material mixture obtained by mixing a material containing cerium oxide (also referred to as cerium raw material) and a material containing zirconium oxide (also referred to as zirconium raw material) at a predetermined ratio was melted at a temperature equal to or higher than the melting point. Later, the obtained melt is cooled to form an ingot, and then, if desired, the ingot is pulverized into a powder. Subsequently, the distortion in the powder crystal is removed under heating, Further, those obtained by finely pulverizing can be mentioned.
- the cerium raw material is not particularly limited, but cerium oxide is preferable.
- the cerium oxide may be an oxide obtained from nitrate, carbonate, sulfate, acetate, chloride, bromide or the like.
- the zirconium element material containing a zirconium oxide such as a badelite, desiliconized zirconia, a zirconium oxide, is preferable.
- the zirconium oxide may be an oxide obtained from nitrate, carbonate, sulfate, acetate, chloride, bromide or the like.
- cerium raw material and the zirconium raw material may be a mixture of these raw materials or a composite oxide.
- the purity of the cerium raw material and the zirconium raw material is not particularly limited, but a purity of 99.9% or more is preferable.
- the above cerium raw material and zirconium raw material are mixed at a predetermined ratio and charged into a melting apparatus.
- the composition is a molar ratio of zirconium atom to cerium atom in the composite oxide (zirconium / cerium), preferably 5/95 to 70/30, more preferably 20/80 to 65/35, and particularly preferably 40/60. It is in the range of 60/40. Outside this range, the desired oxygen storage / release performance and heat resistance cannot be obtained.
- the melting method is not particularly limited as long as at least one kind of the raw material mixture is melted, and examples thereof include an arc method and a high-frequency thermal plasma method.
- a general electromelting method that is, a melting method using an arc electric furnace can be preferably used.
- the mixed cerium raw material and zirconium raw material can be used as a conductive material to promote initial energization.
- a predetermined amount of coke is added.
- the secondary voltage is set to 70 to 100 V
- the average load power is set to 80 to 100 kW
- the heating is performed at a temperature of 2400 ° C. or higher.
- the holding time in the molten state is preferably 1 to 2 hours.
- the atmosphere at the time of melting is not particularly limited, and the atmosphere is not only in the air but also in an inert gas such as nitrogen, argon, or helium. Further, the pressure is not particularly limited, and any of normal pressure, pressurization, and reduced pressure may be used, but the reaction can usually be performed under atmospheric pressure.
- the method for cooling the melt is not particularly limited, it is usually taken out from the melting apparatus and allowed to cool in the atmosphere to 100 ° C. or less, preferably 50 ° C. or less, particularly preferably room temperature. As a result, an ingot of a cerium-zirconium composite oxide in which the cerium raw material and the zirconium raw material are uniform can be obtained.
- the melted ingot is crushed.
- the ingot is not particularly limited, but can be pulverized by a pulverizer such as a jaw crusher or a roll crusher. In consideration of handling in a subsequent process, it is preferable to grind and classify the ingot until it becomes a powder of 3 mm or less, and further 1 mm or less.
- the obtained powder is magnetically separated to separate impurities and then put into an electric furnace, etc., if desired.
- Suboxides in the melting process and distortion in the crystal due to supercooling are removed by oxidative heat treatment. can do.
- the conditions for the oxidation heat treatment are not particularly limited as long as the ingot or the powder is oxidized, but the heat treatment can usually be performed at 100 to 1000 ° C., preferably 600 to 800 ° C.
- the heat treatment time is not particularly limited, but can be 1 to 5 hours, preferably 1 to 3 hours.
- the powder obtained by the above method can be further pulverized according to the application.
- the fine pulverization is not particularly limited, but the fine pulverization can be performed with a pulverizer such as a planetary mill, a ball mill or a jet mill for 5 to 30 minutes.
- the average particle size of the cerium-zirconium composite oxide is preferably 0.2 to 10 ⁇ m, more preferably 1.0 to 5.0 ⁇ m.
- the “melting method-derived cerium-zirconium composite oxide” of the present invention may contain one or more rare earth oxides (excluding cerium oxide). This can be dealt with by adding one or more rare earth oxides (excluding cerium oxide) during the production of “-zirconium composite oxide”.
- rare earth oxides include oxides of lanthanoid elements such as Y, Sc, and La, Pr, and Nd. One or more of these are preferably 1 to 50%, more preferably 3 to 20 % Can be contained.
- wet process-derived cerium dioxide is not particularly limited, but was produced by adding an alkali to a cerium salt-containing solution to form cerium hydroxide and then heat-treating it. Thing and its equivalent.
- urea or the like may be added to the cerium salt-containing solution and heated to produce ammonia to produce cerium hydroxide.
- the crystallite diameter of the “cerium-zirconium composite oxide derived from the melting method” is less than 50 nm, the melting does not proceed sufficiently and good crystallinity cannot be obtained. In such a case, the balance between surface energy and internal energy is biased toward the surface energy side, which is disadvantageous for the movement of lattice oxygen.
- crystallite diameter of “cerium dioxide derived from the wet method” is 50 nm or more, the balance between the surface energy and the internal energy is biased toward the internal energy side, and sufficient surface activity cannot be obtained because it acts as an oxygen release point. Is not preferable.
- the OSC (600 ° C.) of the cerium oxide-zirconium oxide composite oxide of the present invention is preferably 150 ⁇ mol / g or more, more preferably 250 ⁇ mol / g or more, and particularly preferably 280 ⁇ mol / g or more.
- OSC 600 ° C.
- OSC means a value obtained from oxygen consumption at 600 ° C. in the OSC measurement method described later.
- the OSC (600 ° C.) is less than 150 ⁇ mol / g, it is not preferable because it is small for use as an OSC material for automobile catalysts.
- (1) :( 2) (weight ratio) preferably 20 to 99: 1 to 80, more preferably 50 to 90:10 to 50, particularly Preferably, it is 60 to 80:20 to 40.
- the amount of OSC that can be used is not more than 150 ⁇ mol / g, and if it exceeds 99%, the surface activity is low and the temperature characteristics of the OSC ability are lowered. Therefore, it is not preferable.
- cerium oxide-zirconium oxide composite oxide of the present invention may contain 1 to 50%, more preferably 3 to 20%, of one or more rare earth oxides (excluding cerium oxide).
- rare earth oxides include oxides of lanthanoid elements such as Sc, Y, and La, Pr, and Nd, and are preferably oxides of La, Pr, Nd, and Y.
- the cerium-zirconium composite oxide derived from the melting method and (2) the cerium dioxide derived from the wet method are mixed together. (Kojien 2nd revised edition, 4th edition issued on October 15, 1979) ”.
- “(1) Melting method-derived cerium-zirconium composite oxide” with “(2) Wet method-derived cerium dioxide” attached or covered, or “(1) Melting method-derived The cerium-zirconium composite oxide of “(2) wet process-derived cerium dioxide” is exemplified, and a part thereof may be solid solution.
- FIG. 3 shows changes in OSC (600 ° C.) when the weight ratio of “(1) cerium-zirconium composite oxide derived from the melting method and (2) cerium dioxide derived from the wet method” is changed.
- the OSC (600 ° C.) is larger when mixed with each other than with each of them.
- FIG. 7 shows that when “(1) cerium-zirconium composite oxide derived from melting method and (2) cerium dioxide derived from wet method are mixed”, “cerium dioxide derived from wet method and cerium oxide derived from wet method” H 2 -TPR measurement results when “mixed with zirconium oxide in a solid solution” and when “mixed cerium-zirconium composite oxide derived from wet method and cerium dioxide derived from wet method” Show.
- the case where “(1) the cerium-zirconium composite oxide derived from the melting method and (2) the cerium dioxide derived from the wet method are mixed” is more than the case where the two types derived from the wet method are mixed. It can be seen that the desorption of oxygen from the oxide surface starts from a lower temperature, and then the oxidation of hydrogen starts, and the OSC (600 ° C.) is also large.
- the method for producing a cerium oxide-zirconium oxide composite oxide of the present invention is obtained by dispersing and neutralizing a cerium-zirconium composite oxide derived from a melting method in a cerium-containing solution. Thereafter, heat treatment is performed.
- the crystallite diameter of the “cerium-zirconium composite oxide derived from the melting method” is preferably 50 nm or more, more preferably 80 nm or more, and particularly preferably 100 nm or more.
- the cerium salt may be either a first cerium salt or a second cerium salt as long as it supplies cerium ions.
- cerium sulfate, cerium chloride, cerium nitrate or the like is used singly or in combination. be able to.
- the concentration of the cerium salt is not particularly limited, but generally it is preferably 5 to 200 g, particularly 50 to 100 g as cerium oxide (CeO 2 ) in 1000 g of the solvent.
- the molar ratio of zirconium atoms to cerium atoms (zirconium / cerium) in the composite oxide prepared by the above method is 5/95 to 70/30, and the average particle size is 0.2 to 10 ⁇ m, preferably In which 1.0 to 5.0 ⁇ m of “cerium-zirconium composite oxide derived from the melting method” is dispersed in a cerium salt solution.
- the slurry concentration of the “cerium-zirconium composite oxide derived from the melting method” is not particularly limited, but generally it is preferably 50 to 500 gm, particularly 200 to 400 g in 1000 g of the cerium salt solution.
- the “melting method-derived cerium-zirconium composite oxide” of the present invention may contain one or more rare earth oxides (excluding cerium oxide). This can be dealt with by adding one or more rare earth oxides (excluding cerium oxide) during the production of “zirconium composite oxide”.
- the “cerium-zirconium based composite oxide” of the present invention may contain one or more rare earth oxides (excluding cerium oxide).
- the rare earth metal salt This can be dealt with by adding at least one of (excluding cerium salt).
- the alkali used in the present invention is not particularly limited, and for example, ammonium hydroxide, ammonium bicarbonate, sodium hydroxide, potassium hydroxide and the like can be used.
- the amount of alkali added is not particularly limited as long as a precipitate can be generated from the solution, and the pH of the solution is usually 9 or more, preferably 11 or more, more preferably 12 or more.
- the upper limit of the pH is not particularly limited, but is about 14.
- urea may be added, and neutralization may be performed by generating ammonia by heating.
- a feature of the present invention is that this neutralization step, that is, neutralizing a solution in which two components of a solid “cerium-zirconium composite oxide derived from a melting method” and an ionic cerium salt (cerium cerium ion) coexist.
- a composite hydroxide in which a cerium-zirconium composite oxide derived from a melting method and cerium hydroxide derived from a wet method are mixed can be obtained.
- the precipitate formed of “composite hydroxide in which cerium-zirconium composite oxide derived from the melting method and cerium hydroxide derived from the wet method are mixed” is recovered by a solid-liquid separation method.
- the solid-liquid separation method may follow a known method such as filtration, centrifugation, or decantation. After recovery, it is preferable to wash the “composite hydroxide in which the cerium-zirconium composite oxide derived from the melting method and the cerium hydroxide derived from the wet method coexist” with water as necessary to remove the adhering impurities. .
- the obtained “composite hydroxide in which the cerium-zirconium composite oxide derived from the melting method and the cerium hydroxide derived from the wet method are mixed” may be further dried as necessary.
- the drying method may follow a well-known method, for example, any of natural drying, heat drying, etc. may be sufficient. If necessary, a pulverization process, a classification process, or the like may be performed after the drying process.
- the crystallite diameter of “cerium dioxide derived from a wet process” is preferably less than 50 nm, more preferably 30 nm or less, and particularly preferably 20 nm or less.
- the heat treatment temperature is not particularly limited, but it is usually about 1 to 5 hours at about 400 to 900 ° C.
- the heat treatment atmosphere is not particularly limited, it may be usually in the air or an oxidizing atmosphere.
- the composite oxide obtained in this way can be pulverized as necessary. Although it does not specifically limit about grinding
- Average particle diameter (D50) Measurement was performed with a laser diffraction scattering apparatus (LA-950, manufactured by Horiba, Ltd.).
- the average particle diameter (D50) means a particle diameter at which the cumulative frequency of the measured particle diameter distribution is 50% by volume.
- H 2 -TPR H 2 -TPR was determined by using a temperature reduction method (BEL JAPAN INC., MULTITASK TPR).
- 0.1 g of the powder was heated to 300 ° C. and kept in high purity oxygen gas for 60 minutes for sufficient oxidation.
- a 5% hydrogen-argon gas stream 100 sccm
- the sample is heated from 100 ° C. to 900 ° C. at a rate of 10 ° C./min, and the hydrogen consumed during this time is continuously measured with a quadrupole mass spectrometer.
- a water vapor generation curve H 2 -TPR
- Oxygen storage capacity (OSC (600 ° C)) OSC is expressed in ⁇ mol-O 2 / g, that is, oxygen storage capacity per unit weight of the powder.
- 0.50 g of the powder was reduced in a 5% hydrogen-argon stream at 600 ° C. for 10 minutes.
- pulse injection of oxygen gas (0.5 ml per 0.1 second) was performed, and the oxygen gas concentration at the outlet was detected by gas chromatography (Shimadzu Co., LTD., GC-8A). That is, at 600 ° C., oxygen was desorbed with 5% H 2 gas, the amount of oxygen stored (consumed) by injection of oxygen pulse was measured, and the oxygen consumption at 600 ° C. was defined as OSC (600 ° C.).
- Crystallite diameters CeO 2 and CeZrO 4 crystallite diameters were determined by X-ray diffraction analysis (XRD) using an automatic X-ray diffractometer.
- XRD X-ray diffraction analysis
- cerium-zirconium composite oxide derived from the melting method A high-purity zirconium oxide (purity 99.9%) is used as a Zr raw material, and a high-purity cerium oxide (purity 99.9%) is used as a Ce raw material. A powder was produced.
- high-purity zirconium oxide (4.2 kg) and high-purity cerium oxide (5.8 kg) are separated and mixed, using an arc electric furnace, secondary voltage 85 V, average load power 99.5 kW, energization time 1 hour 50 minutes, total electric power 182 kWh was applied, and melting was performed at 2200 ° C. or higher.
- this solution was neutralized with 250 g of 25% aqueous ammonia.
- the pH at this time was 9.3.
- the solution was heated to 50 ° C. and kept for 1 hour.
- a hydroxide was obtained by filtration and washing with water.
- This hydroxide was calcined at 700 ° C. for 10 hours to obtain cerium dioxide powder. Using this powder, D50, SSA, CeO 2 crystallite diameter, OSC (600 ° C.) and the like shown in Table 1 were measured in the same manner as in Example 1.
- a cerium oxide-zirconium oxide composite oxide in which “(1) a cerium-zirconium composite oxide derived from a melting method and (2) cerium dioxide derived from a wet method” are mixed is obtained. I know that.
- Example 1 and Example 2 the crystallite diameter is about 1 ⁇ 2 of the original (Comparative Example 1). The reason for this is not clear, but a single coarse crystal, “cerium-zirconium composite oxide derived from the melting method” and “cerium dioxide derived from the wet method” were mixed and then pulverized. As a result, the coarse crystals are subdivided, and the crystallite diameter is apparently small.
- OSC is activated in two aspects: the reaction of oxidized and reduced molecules on the particle surface (referred to as the reaction process) and the movement / fixation of oxygen within the particle, that is, lattice oxygen (hereinafter referred to as the transfer process).
- the reaction process the reaction of oxidized and reduced molecules on the particle surface
- the transfer process the movement / fixation of oxygen within the particle, that is, lattice oxygen
- the crystallinity is good (Zr is completely inserted into the Ce skeleton), and increasing the crystallite size leads to activation.
- this activation is because the surface is inactive in the reaction process.
- the temperature at which lattice oxygen can be used is limited to high temperatures. The details of this cause are thought to be largely influenced by the fact that the reaction field (reaction cross section) is reduced due to the lower specific surface area.
- the OSC ability of the OSC material is increased by realizing a dual structure with respect to the above-mentioned trade-off problem in the activation, thereby simultaneously realizing a lowering of the lattice energy transfer energy and securing of the reaction field. It is made available without being limited to.
- the obtained hydroxide was baked in air at 650 ° C. for 5 hours to obtain an oxide.
- Example 2 D50, SSA, CeO 2 crystallite diameter, CZ crystallite diameter, OSC (600 ° C.) and the like shown in Table 2 were measured in the same manner as in Example 1.
- the reaction solution was aged by heating to 95 ° C. and holding for 0.5 hour. Next, after the aged solution was cooled to room temperature, 414 g of a cerium nitrate solution that was 20% in terms of CeO 2 was added and mixed uniformly. 25% sodium hydroxide was added to the obtained mixed solution and neutralized until the pH became 13 or more to generate a hydroxide precipitate. The obtained hydroxide precipitate was filtered and thoroughly washed with water. After washing with water, the hydroxide was calcined at 600 ° C. for 5 hours in the atmosphere, and the resulting oxide was pulverized to 20 ⁇ m or less to obtain a wet process-derived cerium-zirconium composite oxide.
- wet process-derived CeO 2 50: 50 (weight ratio)>
- the wet process-derived cerium-zirconium composite oxide prepared above was pulverized into 350 g of 20% cerium nitrate solution (CeO 2 conversion: 70 g), and 70 g of an average particle size of 2.0 ⁇ m was added. A slurry containing the derived cerium-zirconium composite oxide was obtained.
- this solution was neutralized with 250 g of 25% aqueous ammonia.
- the pH at this time was 10.0.
- the solution was heated to 50 ° C. and kept for 1 hour.
- a hydroxide was obtained by filtration and washing with water.
- a composite oxide “a mixture of a cerium-zirconium composite oxide derived from a wet process and a cerium dioxide derived from a wet process” could be produced.
- Example 2 D50, SSA, CeO 2 crystallite diameter, CZ crystallite diameter, OSC (600 ° C.) and the like shown in Table 2 were measured in the same manner as in Example 1.
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Abstract
Description
1.(1)溶融法由来のセリウム-ジルコニウム複合酸化物と(2)湿式法由来の二酸化セリウムとを混在させたことを特徴とする酸化セリウム-酸化ジルコニウム系複合酸化物。
2.溶融法由来のセリウム-ジルコニウム複合酸化物の結晶子径が50nm以上で、湿式法由来の二酸化セリウムの結晶子径が50nm未満である、前記1に記載の酸化セリウム-酸化ジルコニウム系複合酸化物。
3.OSC(600℃)が150μmol/g以上である、前記1又は2に記載の酸化セリウム-酸化ジルコニウム系複合酸化物。
4.(1):(2)(重量比)=20~99:1~80である、前記1~3のいずれかに記載の酸化セリウム-酸化ジルコニウム系複合酸化物。
5.溶融法由来のセリウム-ジルコニウム複合酸化物が、稀土類酸化物(酸化セリウムを除く)の1種以上を含む、前記1~4のいずれかに記載の酸化セリウム-酸化ジルコニウム系複合酸化物。
6.酸化セリウム-酸化ジルコニウム系複合酸化物が、稀土類酸化物(酸化セリウムを除く)の1種以上を含む、前記1~5のいずれかに記載の酸化セリウム-酸化ジルコニウム系複合酸化物。
7.セリウム含有溶液に溶融法由来のセリウム-ジルコニウム複合酸化物を分散させ、中和した後、熱処理することを特徴とする酸化セリウム-酸化ジルコニウム系複合酸化物の製造方法。
8.セリウム含有溶液が、稀土類金属塩(セリウム塩を除く)の1種以上を含む、前記7に記載の酸化セリウム-酸化ジルコニウム系複合酸化物の製造方法。
9.溶融法由来のセリウム-ジルコニウム複合酸化物の結晶子径が50nm以上である、前記7又は8に記載の酸化セリウム-酸化ジルコニウム系複合酸化物の製造方法。
10.溶融法由来のセリウム-ジルコニウム複合酸化物が、稀土類酸化物(酸化セリウムを除く)の1種以上を含む、前記7~9のいずれかに記載の酸化セリウム-酸化ジルコニウム系複合酸化物の製造方法。
本発明の酸化セリウム-酸化ジルコニウム系複合酸化物は、「(1)溶融法由来のセリウム-ジルコニウム複合酸化物と(2)湿式法由来の二酸化セリウムとを混在させた」ことを特徴とする。
本発明の酸化セリウム-酸化ジルコニウム系複合酸化物の製造方法は、セリウム含有溶液に溶融法由来のセリウム-ジルコニウム複合酸化物を分散させ、中和した後、熱処理することを特徴とする。
(1)平均粒径(D50)
レーザー回折散乱装置(堀場製作所製LA-950)で測定した。
なお、本発明において、平均粒径(D50)とは測定した粒子径分布の累積頻度が50体積%となる粒子径をいう。
比表面積計(「フローソーブ-II」マイクロメリティクス製)を用い、BET法により測定した。
H2-TPRは、昇温還元法(BEL JAPAN INC.,MULTITASK T.P.R.)を用いることにより求めた。
OSCは、μmol-O2/g、つまり粉末の単位重量当りの酸素吸蔵容量で表す。まず、粉末0.50gを5%の水素-アルゴン気流中600℃、10分で還元処理した。次に、酸素ガスのパルス注入(0.1秒に0.5ml)を行い、出口の酸素ガス濃度をガスクロマトグラフィー(Shimadzu Co.,LTD.,GC-8A)で検出した。即ち、600℃において、5%H2ガスによって酸素離脱を行い、酸素パルスの注入で吸蔵(消費)される酸素量を測定し、600℃での酸素消費量をOSC(600℃)とした。
CeO2及びCeZrO4結晶子径は、自動X線回折装置を用い、X線回折分析(XRD)を行い求めた。X線源には、Cuターゲットを用いて、20°≦2θ≦60°の範囲について測定を行い、2θ=28.6°、29.3°のピークの値をもとに、Sheller法から結晶子径を算出した。
Zrの原料として高純度酸化ジルコニウム(純度99.9%)を、Ceの原料として高純度酸化セリウム(純度99.9%)を用い、以下に示す手順に従って溶融法由来のセリウム-ジルコニウム複合酸化物粉末を製造した。
<溶融法由来CZ:湿式法由来CeO2=75:25(重量比)の製造>
20%硝酸第一セリウム溶液350g(CeO2換算:70g)に上記で製造した溶融法由来のセリウム-ジルコニウム複合酸化物210gを添加し、溶融法由来のセリウム-ジルコニウム複合酸化物含有スラリーを得た。
<溶融法由来CZ:湿式法由来CeO2=50:50(重量比)の製造>
溶融法由来のセリウム-ジルコニウム複合酸化物の添加量を70gにした以外は実施例1と同じ処理を行った。
上記で得られた溶融法由来のセリウム-ジルコニウム複合酸化物を700℃で5時間焼成したものをそのまま使用し、実施例1と同様にして表1に示すD50、SSA、CZ結晶子径及びOSC(600℃)等を測定した。
硝酸セリウム(IV)溶液(CeO2として100g含有)412.5gへ純水を986g、硝酸(100%換算)を30.3g、尿素を600g添加した(水酸化セリウムとするのに必要な量の8.4倍)。
20%硝酸第一セリウム溶液280g(CeO2換算:56g含有)を85℃まで加熱し、25%硫酸ナトリウム溶液624g(Na2SO4換算:156g含有)を添加後、85℃で1時間保持し、硫酸第一セリウムナトリウム複塩含有スラリーを得た。
<湿式法由来セリウム-ジルコニウム複合酸化物の製造>
25%硫酸ナトリウム溶液141gを85℃に昇温し、これに予め85℃に加温したZrO2換算16%となるオキシ塩化ジルコニウム溶液375gを添加した後、フリー酸濃度が1.5Nになるように塩酸を加え、0.5時間保持し、塩基性硫酸ジルコニウムを生成させた。
20%硝酸第一セリウム溶液350g(CeO2換算:70g)に上記で製造した湿式法由来セリウム-ジルコニウム複合酸化物を粉砕し、平均粒径を2.0μmとしたもの70gを添加し、湿式法由来セリウム-ジルコニウム複合酸化物含有スラリーを得た。
Claims (10)
- (1)溶融法由来のセリウム-ジルコニウム複合酸化物と(2)湿式法由来の二酸化セリウムとを混在させたことを特徴とする酸化セリウム-酸化ジルコニウム系複合酸化物。
- 溶融法由来のセリウム-ジルコニウム複合酸化物の結晶子径が50nm以上で、湿式法由来の二酸化セリウムの結晶子径が50nm未満である、請求項1に記載の酸化セリウム-酸化ジルコニウム系複合酸化物。
- OSC(600℃)が150μmol/g以上である、請求項1又は2に記載の酸化セリウム-酸化ジルコニウム系複合酸化物。
- (1):(2)(重量比)=20~99:1~80である、請求項1~3のいずれかに記載の酸化セリウム-酸化ジルコニウム系複合酸化物。
- 溶融法由来のセリウム-ジルコニウム複合酸化物が、稀土類酸化物(酸化セリウムを除く)の1種以上を含む、請求項1~4のいずれかに記載の酸化セリウム-酸化ジルコニウム系複合酸化物。
- 酸化セリウム-酸化ジルコニウム系複合酸化物が、稀土類酸化物(酸化セリウムを除く)の1種以上を含む、請求項1~5のいずれかに記載の酸化セリウム-酸化ジルコニウム系複合酸化物。
- セリウム含有溶液に溶融法由来のセリウム-ジルコニウム複合酸化物を分散させ、中和した後、熱処理することを特徴とする酸化セリウム-酸化ジルコニウム系複合酸化物の製造方法。
- セリウム含有溶液が、稀土類金属塩(セリウム塩を除く)の1種以上を含む、請求項7に記載の酸化セリウム-酸化ジルコニウム系複合酸化物の製造方法。
- 溶融法由来のセリウム-ジルコニウム複合酸化物の結晶子径が50nm以上である、請求項7又は8に記載の酸化セリウム-酸化ジルコニウム系複合酸化物の製造方法。
- 溶融法由来のセリウム-ジルコニウム複合酸化物が、稀土類酸化物(酸化セリウムを除く)の1種以上を含む、請求項7~9のいずれかに記載の酸化セリウム-酸化ジルコニウム系複合酸化物の製造方法。
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014030800A (ja) * | 2012-08-03 | 2014-02-20 | Noritake Co Ltd | 自動車排ガス浄化用助触媒材およびその製造方法 |
JP2014030801A (ja) * | 2012-08-03 | 2014-02-20 | Noritake Co Ltd | 自動車排ガス浄化用助触媒材およびその製造方法 |
JP2015034113A (ja) * | 2013-08-09 | 2015-02-19 | 株式会社豊田中央研究所 | セリア−ジルコニア系複合酸化物及びその製造方法、並びにそのセリア−ジルコニア系複合酸化物を用いた排ガス浄化用触媒 |
WO2015087781A1 (ja) * | 2013-12-09 | 2015-06-18 | 株式会社キャタラー | 排ガス浄化用触媒 |
Families Citing this family (4)
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JP5816648B2 (ja) * | 2013-04-18 | 2015-11-18 | 三井金属鉱業株式会社 | 排気ガス浄化用触媒組成物及び排気ガス浄化用触媒 |
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EP3436409B1 (en) | 2016-04-01 | 2024-05-29 | Pacific Industrial Development Corporation | Method of making mesoporous zirconium-based mixed oxides and product obtained thereby |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005314134A (ja) | 2004-04-27 | 2005-11-10 | Toyota Motor Corp | 金属酸化物粒子及びその製造方法、並びに排ガス浄化触媒 |
WO2006030763A1 (ja) | 2004-09-16 | 2006-03-23 | Daiichi Kigenso Kagaku Kogyo Co., Ltd. | セリウム-ジルコニウム系複合酸化物、その製造方法、それを用いた酸素吸蔵放出材料、排気ガス浄化触媒、及び排気ガス浄化方法 |
WO2008004452A1 (fr) * | 2006-07-06 | 2008-01-10 | Cataler Corporation | Matière de stockage d'oxygène |
JP2008013423A (ja) | 2006-06-30 | 2008-01-24 | Daiichi Kigensokagaku Kogyo Co Ltd | 酸化セリウム−酸化ジルコニウム系複合酸化物及びその製造方法 |
WO2008093471A1 (ja) * | 2007-02-01 | 2008-08-07 | Daiichi Kigenso Kagaku Kogyo Co., Ltd. | 自動車用排気ガス浄化装置に用いられる触媒系、それを用いた排気ガス浄化装置、及び排気ガス浄化方法 |
WO2010064497A1 (ja) * | 2008-12-03 | 2010-06-10 | 第一稀元素化学工業株式会社 | 排気ガス浄化触媒、それを用いた排気ガス浄化装置、及び排気ガス浄化方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005102523A1 (en) | 2004-04-27 | 2005-11-03 | Toyota Jidosha Kabushiki Kaisha | Process for producing metal oxide particle and exhaust gas purifying catalyst |
JP4123185B2 (ja) * | 2004-04-27 | 2008-07-23 | トヨタ自動車株式会社 | 金属酸化物粒子の製造方法 |
JP4789794B2 (ja) * | 2005-12-28 | 2011-10-12 | 第一稀元素化学工業株式会社 | セリウム・ジルコニウム複合酸化物及びその製造方法 |
-
2011
- 2011-02-25 WO PCT/JP2011/054309 patent/WO2011108457A1/ja active Application Filing
- 2011-02-25 JP JP2012503110A patent/JP5748739B2/ja active Active
- 2011-02-25 CN CN201180012112.3A patent/CN102781840B/zh active Active
- 2011-02-25 US US13/577,375 patent/US8765631B2/en active Active
- 2011-02-25 EP EP11750567.7A patent/EP2543638B1/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005314134A (ja) | 2004-04-27 | 2005-11-10 | Toyota Motor Corp | 金属酸化物粒子及びその製造方法、並びに排ガス浄化触媒 |
WO2006030763A1 (ja) | 2004-09-16 | 2006-03-23 | Daiichi Kigenso Kagaku Kogyo Co., Ltd. | セリウム-ジルコニウム系複合酸化物、その製造方法、それを用いた酸素吸蔵放出材料、排気ガス浄化触媒、及び排気ガス浄化方法 |
JP2008013423A (ja) | 2006-06-30 | 2008-01-24 | Daiichi Kigensokagaku Kogyo Co Ltd | 酸化セリウム−酸化ジルコニウム系複合酸化物及びその製造方法 |
WO2008004452A1 (fr) * | 2006-07-06 | 2008-01-10 | Cataler Corporation | Matière de stockage d'oxygène |
WO2008093471A1 (ja) * | 2007-02-01 | 2008-08-07 | Daiichi Kigenso Kagaku Kogyo Co., Ltd. | 自動車用排気ガス浄化装置に用いられる触媒系、それを用いた排気ガス浄化装置、及び排気ガス浄化方法 |
WO2010064497A1 (ja) * | 2008-12-03 | 2010-06-10 | 第一稀元素化学工業株式会社 | 排気ガス浄化触媒、それを用いた排気ガス浄化装置、及び排気ガス浄化方法 |
Non-Patent Citations (2)
Title |
---|
"Kojien", 15 October 1979 |
See also references of EP2543638A4 |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014030800A (ja) * | 2012-08-03 | 2014-02-20 | Noritake Co Ltd | 自動車排ガス浄化用助触媒材およびその製造方法 |
JP2014030801A (ja) * | 2012-08-03 | 2014-02-20 | Noritake Co Ltd | 自動車排ガス浄化用助触媒材およびその製造方法 |
JP2015034113A (ja) * | 2013-08-09 | 2015-02-19 | 株式会社豊田中央研究所 | セリア−ジルコニア系複合酸化物及びその製造方法、並びにそのセリア−ジルコニア系複合酸化物を用いた排ガス浄化用触媒 |
US10065179B2 (en) | 2013-08-09 | 2018-09-04 | Toyota Jidosha Kabushiki Kaisha | Ceria-zirconia-based composite oxide and method for producing same, and exhaust gas purification catalyst including ceria-zirconia-based composite oxide |
US10913051B2 (en) | 2013-08-09 | 2021-02-09 | Toyota Jidosha Kabushiki Kaisha | Ceria-zirconia-based composite oxide and method for producing same, and exhaust gas purification catalyst including ceria-zirconia-based composite oxide |
WO2015087781A1 (ja) * | 2013-12-09 | 2015-06-18 | 株式会社キャタラー | 排ガス浄化用触媒 |
JPWO2015087781A1 (ja) * | 2013-12-09 | 2017-03-16 | 株式会社キャタラー | 排ガス浄化用触媒 |
US9849441B2 (en) | 2013-12-09 | 2017-12-26 | Cataler Corporation | Exhaust gas purifying catalyst |
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