POROUS CERAMIC STRUCTURAL BODY
20170274357 · 2017-09-28
Assignee
Inventors
Cpc classification
B01J2523/00
PERFORMING OPERATIONS; TRANSPORTING
B01D53/9413
PERFORMING OPERATIONS; TRANSPORTING
F01N2330/30
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
B01J23/002
PERFORMING OPERATIONS; TRANSPORTING
B01D2258/012
PERFORMING OPERATIONS; TRANSPORTING
B01J2523/00
PERFORMING OPERATIONS; TRANSPORTING
F01N3/2828
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F01N2330/06
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
B01J21/10
PERFORMING OPERATIONS; TRANSPORTING
B01D2257/404
PERFORMING OPERATIONS; TRANSPORTING
International classification
Abstract
A honeycomb structure is formed of a porous ceramic material and has pores in the structural body, wherein cerium dioxide is present in a state that it is incorporated in the structural body in the ceramic material, and at least a part of cerium dioxide particles is exposed on pore surfaces of the pores. The ceramic material includes cordierite or silicon carbide as a major component, the ratio of the cerium dioxide to the ceramic material is in the range of from 1.0% by mass to 10.0% by mass, and at least a part of catalyst particulates of a platinum group element such as platinum or palladium is loaded by the cerium dioxide particles.
Claims
1. A porous ceramic structural body formed by a porous ceramic material and having pores in the structural body, wherein the ceramic material is present in a state that cerium dioxide is incorporated in the structural body, and at least a part of the cerium dioxide is exposed on the pore surfaces of the pores.
2. The porous ceramic structural body according to claim 1, wherein the ratio of the cerium dioxide to the ceramic material is in the range of from 1.0% by mass to 10.0% by mass.
3. The porous ceramic structural body according to claim 1, wherein the ceramic material comprises either one of cordierite or silicon carbide as a major component.
4. The porous ceramic structural body according to claim 1, further comprising catalyst particulates of a platinum group element distributed on the pore surfaces, wherein at least a part of the catalyst particulates is loaded by the particles of the cerium dioxide exposed on the pore surfaces.
5. The porous ceramic structural body according to claim 4, wherein the catalyst of the platinum group element is either one of platinum or palladium.
6. The porous ceramic structural body according to claim 1, wherein the porous ceramic structural body is a honeycomb structure.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0030]
[0031]
[0032]
[0033]
[0034]
[0035]
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0036] The embodiments of the porous ceramic structural body of the present invention will be mentioned below in detail with referring to the drawings. However, the porous ceramic structural body of the present invention is not limited to the following embodiments, and various modification, correction, and improvement of designing and the like can be added thereto as long as the embodiments do not deviate from the scope of the present invention.
[0037] As shown in
[0038] As the ceramic material that forms the honeycomb structure 1 (partition walls 4), a well-known porous material is envisaged, and examples include ceramic materials containing as a major component, silicon carbide, silicon-silicon carbide (Si/SiC)-based composite materials, cordierite, mullite, alumina, spinel, silicon carbide-cordierite-based composite materials, lithium aluminum silicate and aluminum titanate. However, the porous ceramic structural body of the present invention is not limited to the above-mentioned honeycomb structure 1 and may have various shapes. Furthermore, even in the case when the porous ceramic structural body has a honeycomb shape, the porous ceramic structural body is not limited to an approximately round pillar-shaped porous ceramic structural body.
[0039] The rate (content rate) of the cerium dioxide contained in the porous ceramic material that constitutes the honeycomb structure 1 of this exemplary embodiment is in the range of from 1.0% by mass to 10.0% by mass, further preferably in the range of from 2.5% by mass to 6.0% by mass. In the case when the rate of the cerium dioxide is lower than 1.0% by mass, the number of the cerium dioxide particles 6 that are exposed on the pore surfaces 5a decreases, and thus a loading amount of catalyst particulates 7 by the particles 6 on the pore surfaces 5a mentioned below is small. As a result, it becomes difficult to load the catalyst in an amount sufficient to obtain high catalyst activity.
[0040] On the other hand, when the rate of the cerium dioxide is more than 10.0% by mass, the particles 6 that are exposed on the pore surfaces 5a increase. Therefore, a part of the pores 5 is clogged by the exposed particles 6, and thus it is possible that the porosity of the partition wall 4 decreases and defects such as pressure loss occur. Therefore, the rate of the cerium dioxide is limited to the above-mentioned range.
[0041] As mentioned above, the honeycomb structure 1 of this exemplary embodiment is formed in a way such that the cerium dioxide particles 6 are exposed on the surfaces of the plural pores 5 formed in the structural body of the partition walls 4. By this way, a part of the catalyst particulates 7 is selectively loaded by the particles 6. That is, it is not necessary to increase the specific surface area by a conventional coat treatment (wash coat) with γ-alumina, and thus the loading amount of the catalyst can be easily increased. Accordingly, defects such as decrease in pressure loss by a coat treatment with γ-alumina do not occur.
[0042] The honeycomb structure 1 of this exemplary embodiment further has, in addition to the above-mentioned constitution, catalyst particulates 7 of a platinum group element (ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir) and platinum (Pt)) distributed on the pore surfaces 5a in the partition walls 4. At least a part of the catalyst particulates 7 is selectively loaded by the particle surfaces of the above-mentioned cerium dioxide particles 6 exposed on the pore surfaces 5a (see
[0043] The catalyst particulates 7 loaded by the particles 6 are not specifically limited as long as they are catalyst particulates of a platinum group element as mentioned above, but it is specifically preferable to use platinum (Pt) or palladium (Pd). These platinum and palladium have been generally used since before as catalysts for purification treatment of NO.sub.2. Furthermore, as shown in
[0044] According to the honeycomb structure 1 of this exemplary embodiment, the cerium dioxide is present in an incorporated state at a predetermined ratio in the structural body (in the ceramic material) that constitutes said honeycomb structure 1 (partition walls 4), said cerium dioxide particles 6 are exposed on the pore surfaces 5a in the structural body of the partition walls 4, and at least a part of the catalyst particulates 7 such as platinum is selectively loaded by the particles 6. By this way, many catalyst particulates 7 are loaded by the cerium dioxide particles 6 exposed on the pore surfaces 5a. As a result, in the case when the honeycomb structure 1 is used as a catalyst for a purifying treatment of NO.sub.2 or the like, high catalyst activity by the catalyst such as loaded platinum can be exerted, whereby a purification rate (conversion rate) of NO.sub.2 can be improved. Accordingly, the honeycomb structure can be used as a catalyst that does not cause any defects such as decrease in pressure loss.
[0045] The porous ceramic structural body (honeycomb structure) of the present invention will be explained below based on the following Examples, but the porous ceramic structural body of the present invention is not limited to these Examples.
EXAMPLES
[0046] The ceramic materials that constitute the honeycomb structures of Examples 1 to 5 and Comparative Examples 1 to 3 (containing an inorganic raw material, and other raw materials), and the content rates thereof and the like will be shown in the following Table 1. Examples 1 to 4 and Comparative Examples 1 to 3 are honeycomb structures in which the ceramic component is cordierite, and Example 5 is a honeycomb structure constituted by a composite material of silicon/silicon carbide (Si/SiC).
TABLE-US-00001 TABLE 1 Comparative Comparative Comparative Example/Comparative Example Example 1 Example 2 Example 3 Example 4 Example 5 Example 1 Example 2 Example 3 Ceramic component Cordierite Cordierite Cordierite Cordierite Si/SiC Cordierite Cordierite Cordierite Talc % by 39.7 39.7 39.7 0 — 39.7 0 39.7 Magnesium oxide mass 0 0 0 11.9 — 0 11.6 0 α-alumina 14.1 14.1 14.1 33.3 — 14.1 45.0 14.1 Aluminum hydroxide 15.3 15.3 15.3 0 — 15.3 0.0 15.3 Kaolin 17.5 17.5 17.5 0 — 17.5 0.0 17.5 Silica 10.7 8.4 8.4 49.1 — 13.4 43.4 13.4 CeO.sub.2 2.7 5 5 5.7 — 0 0 0 SiC — — — — 80 — — — Si — — — — 20 — — — Total of inorganic raw materials 100 100 100 100 100 100 100 100 Coke parts 2.0 2.0 2.0 2.0 — 2.0 2.0 2.0 Foamable resin by 5.4 5.4 5.4 5.4 — 5.4 5.4 5.4 Water absorbable resin mass 1.5 1.5 1.5 1.5 — 1.5 1.5 1.5 Methyl cellulose resin 5.0 5.0 5.0 5.0 7.0 5.0 5.0 5.0 Aluminum hydroxide — — — — 0.4 — — — Strontium carbonate — — — — 1.4 — — — CeO.sub.2 — — — — 5.0 — — — Starch — — — — 3.5 — — — Sintering temperature ° C. 1400 1400 1375 1400 1450 1425 1425 1425 Sintering atmosphere Air Air Air Air Argon Air Air Air Amount of catalyst g/L 5 5 5 1 5 5 1 1 (Pt) Amount of catalyst 0 0 0 0 0 0 0 10 (CeO.sub.2)
1. Preparation of Honeycomb Structure of Example 1
[0047] (1) Preparation of Kneaded Material
[0048] The inorganic raw materials for a honeycomb structure shown in Table 1 (39.7% by mass of talc, 14.1% by mass of a-alumina, 15.3% by mass of aluminum hydroxide, 17.5% by mass of kaolin, 10.7% by mass of silica and 2.7% by mass of cerium dioxide) are mixed, and as other raw materials, 2.0 parts by mass of coke, 5.4 parts by mass of a foamable resin, 1.5 parts by mass of a water-absorbable resin and 5.0 parts by mass of methyl cellulose are added to 100 parts by mass of the obtained inorganic raw material. The mixture is then mixed for 10 minutes by using a kneader, and 1 part by mass of potassium laurate and 33 parts by mass of water (description in Table 1 is omitted) are added thereto. In the above-mentioned description, the part(s) by mass is based on 100 parts by mass of the inorganic raw material before being mixed with the coke and the like. The mixture is further kneaded by using a kneader for 45 minutes, whereby a flexible kneaded material is prepared.
[0049] (2) Preparation of Honeycomb Formed Body
[0050] The obtained kneaded material is formed into a pillar shape by using a vacuum pug mill, and the product is introduced into an extrusion molding machine to thereby prepare a honeycomb formed body having a honeycomb shape. The honeycomb formed body herein has a honeycomb diameter of 50 mm, a partition wall thickness of 12 mils (about 0.3 mm), a cell density of 300 cpsi (cells per square inches: 46.5 cells/cm.sup.2), and a circumferential wall thickness of about 0.6 mm, and has lattice-like partition walls that define plural cells that serve as flow paths for a fluid inside of the honeycomb formed body.
[0051] (3) Drying and Sintering of Honeycomb Formed Body
[0052] The prepared honeycomb formed body was subjected to microwave drying, then hot air drying (80° C.×12 hours), and the end faces at the both ends of the honeycomb dried body were cut off so that the length of the honeycomb dried body after the drying in the axial direction became 60 mm. The honeycomb dried body was then subjected to a sintering treatment in the air at a sintering temperature of 1400° C., whereby a honeycomb structure on which any catalyst was not loaded was prepared.
[0053] (4) Loading of Catalyst
[0054] The obtained honeycomb structure was immersed in a 4.0% by mass aqueous solution of tetraammine platinum nitrate and dried in the air at a drying temperature of 100° C. for 4 hours. The above-mentioned immersion and drying treatments were repeated until the weight increase became 5 g/L of a platinum content with respect to the original honeycomb structure. The honeycomb structure was then sintered in the air at a sintering temperature of 550° C. By this way, the honeycomb structure of cordierite of Example 1 was obtained.
2. Preparation of Honeycomb Structure of Example 2
[0055] The honeycomb structure of cordierite of Example 2 was prepared under identical conditions to that of the above-mentioned (1) to (4), except that the content rate of the silica in the inorganic raw material in Example 1 was changed to 8.4% by mass and the content rate of the cerium dioxide was changed to 5.0% by mass.
3. Preparation of Honeycomb Structure of Example 3
[0056] The honeycomb structure of cordierite of Example 3 was prepared under identical conditions to that of Example 2, except that the sintering temperature in Example 2 was changed to 1375° C.
[0057] (1) Preparation of Honeycomb Formed Body, Drying and Sintering of Honeycomb Formed Body, and Loading of Catalyst
[0058] The procedures are identical with those of Examples 1 and 2, and thus the explanation is omitted. By this way, the honeycomb structure of cordierite of Example 3 was obtained.
4. Preparation of Honeycomb Structure of Example 4
[0059] (1) Preparation of Kneaded Material
[0060] The plural kinds of inorganic raw materials (11.9% by mass of magnesium oxide, 33.3% by mass of a-alumina, 49.1% by mass of silica, 5.7% by mass of cerium dioxide) for a honeycomb structure shown in Table 1 are mixed, and as other raw materials, 2.0 parts by mass of coke, 5.4 parts by mass of a foamable resin, 1.5 parts by mass of a water-absorbable resin, and 5.0 parts by mass of methyl cellulose are added to 100 parts by mass of the obtained inorganic raw material. The mixture is then mixed for 10 minutes by using a kneader, and 1 part by mass of potassium laurate and 33 parts by mass of water (description in Table 1 is omitted) are added. In the above description, the part(s) by mass is based on the same criterion as that of Example 1. The mixture is further kneaded by using a kneader for 45 minutes, whereby a flexible kneaded material is prepared.
[0061] (2) Preparation of Honeycomb Formed Body, Drying and Sintering of Honeycomb Formed Body, and Loading of Catalyst
[0062] The procedures are identical with those of Examples 1 and 2, and thus the explanation is omitted. However, the catalytic amount of the platinum content was set to be 1 g/L. By this way, the honeycomb structure of cordierite of Example 4 was obtained.
5. Preparation of Honeycomb Structure of Example 5
[0063] (1) Preparation of Kneaded Material
[0064] The two kind of inorganic raw materials for a honeycomb structure shown in Table 1 (80% by mass of silicon carbide (SiC) and 20% by mass of silicon (Si)) are mixed, and 0.4 parts by mass of aluminum hydroxide, 1.4 parts by mass of strontium carbonate, 5.0 parts by mass of cerium dioxide, 3.5 parts by mass of starch and 7.0 parts by mass of a methyl cellulose resin are added to 100 parts by mass of the obtained ceramic material. Thereafter, the mixture is mixed by using a kneader for 10 minutes, and 27% parts by mass of water (the description in Table 1 is omitted) is added thereto. In the above-mentioned description, the 2 0 part(s) by mass is based on 100 parts by mass of the ceramic material as the total of silicon carbide and silicon. The mixture is further kneaded by using a kneader for 45 minutes, whereby a flexible kneaded material is prepared.
[0065] (2) Preparation of Honeycomb Formed Body
[0066] Since the preparation is identical with those in Examples 1 to 4, the explanation is omitted.
[0067] (3) Drying and Sintering of Honeycomb Formed Body
[0068] The prepared honeycomb formed body was subjected to microwave drying, then hot air drying (80° C.×12 hours), and the end faces at the both ends of the honeycomb dried body were cut off so that the length of the honeycomb dried body after the drying in the axial direction became 60 mm. The honeycomb dried body was then subjected to a sintering treatment under argon atmosphere at a sintering temperature of 1450° C., whereby a honeycomb structure on which any catalyst was not loaded was prepared.
[0069] (4) Loading of Catalyst
[0070] The obtained honeycomb structure was immersed in a 4.0% by mass aqueous solution of tetra ammine platinum nitrate, and dried in the air at a drying temperature of 100° C. for 4 hours. The above-mentioned immersion and drying treatment were repeated until the weight increase became 0.1% by mass of a platinum content with respect to the original honeycomb structure. The honeycomb structure was then sintered in the air at a sintering temperature of 550° C. By this way, the honeycomb structure of silicon/silicon carbide (Si/SiC) of Example 5 was obtained.
6. Preparation of Honeycomb Structure of Comparative Example 1
[0071] The honeycomb structure of cordierite of Comparative Example 1 was obtained under identical conditions with those of Example 1, except that cerium dioxide was not added, the content rate of the silica in the raw material was set to 13.4% by mass, and the sintering temperature was preset to 1425° C.
7. Preparation of Honeycomb Structure of Comparative Example 2
[0072] The honeycomb structure of cordierite of Comparative Example 2 was obtained under identical conditions with those of Example 4, except that cerium dioxide was not added, and the content rates in the raw material were set to 11.6% by mass of magnesium oxide, 45.0% by mass of a-alumina and 43.4% by mass of silica.
7. Preparation of Honeycomb Structure of Comparative Example 3
[0073] (1) Preparation of Catalyst
[0074] 24 g of a 4.0% by mass aqueous solution of ammine platinum nitrate was added to 10 g of water, the mixture was stirred by a stirrer for 30 minutes, a cerium dioxide powder was put therein, and the temperature was raised to evaporate the water content while the mixture was stirred. After the water content had been evaporated, the product was dried in the air at a drying temperature of 100° C. for 4 hours, and further sintered in the air at a sintering temperature of 550° C. for 1 hour. The product obtained after the sintering was sieved to give a catalyst.
[0075] (2) Loading of Catalyst
[0076] 4.5 g of the obtained catalyst was added to 100 g of water, and the mixture was stirred by a stirrer, whereby a catalyst liquid was prepared. Subsequently, a honeycomb structure prepared in a similar manner to that of Comparative Example 1 was immersed in said catalyst liquid, and dried in the air at a drying temperature of 100° C. for 4 hours. The above-mentioned immersion and drying treatment were repeated until the weight increase became 1 g/L of a platinum content with respect to the original honeycomb structure. The honeycomb structure was then sintered in the air at a sintering temperature of 550° C. By this way, the honeycomb structure of cordierite of Comparative Example 3 was obtained.
[0077] The following evaluation items: the NO.sub.2 conversion rate, the particle diameter of the cerium dioxide (CeO.sub.2), and the rate of the CeO.sub.2 particles exposed on the pore surfaces, were respectively measured for the prepared honeycomb structures of Examples 1 to 5 and Comparative Examples 1 to 3. The summarization of the measurement result is shown in the following Table 2, and
TABLE-US-00002 TABLE 2 Example/ Example Example Example Example Example Comparative Comparative Comparatve Comparative Example 1 2 3 4 5 Example 1 Example 2 Example 3 NO.sub.2 conversion % 50.1 57.8 32.4 25.0 55.0 27.6 5.0 18.0 rate Particle diameter μm 0.045 0.02 3.0 0.025 2.0 None None <0.05 of CeO.sub.2 Rate of CeO.sub.2 % 11.0 14.8 5.4 2.5 13.6 0.0 None None particles exposed on pore surfaces
[0078] 8. Evaluation Item (NO.sub.2 Conversion Rate)
[0079] Each of the honeycomb structures prepared as above (Examples 1 to 5 and Comparative Examples 1 to 3) was processed into a sample specimen having a diameter (=Φ) of 25.4 mm×a length (=L) of 50.8 mm, and the processed outer periphery was coated with a similar material to that of the substrate. This was evaluated as a measurement sample by using an automobile exhaust gas analyzer. At this time, the above-mentioned measurement sample was set in a reaction tube in a temperature raising furnace and kept at 250° C. On the other hand, a mixing gas with a nitrogen balance of NO (carbon monoxide): 200 ppm and oxygen (O.sub.2): 10% adjusted to a gas temperature of 250° C. was prepared, and introduced into the measurement sample set in the reaction tube. At this time, the gas (exhaust gas) emitted from the measurement sample was analyzed by using an exhaust gas measurement apparatus (manufactured by HORIBA, Ltd.: MEXA-6000FT), and the respective exhaust concentrations (NO concentration and NO.sub.2 concentration) were measured. Based on the measurement results, the NO.sub.2 conversion rate (1-NO concentration/(NO concentration+NO.sub.2 concentration)) was calculated. In the case when the loading amount of platinum was 5 g/L, the sample having the NO.sub.2 conversion rate of 45% or more was evaluated to be “fine”, the sample having the NO.sub.2 conversion rate of 30% or more and lower than 45% was evaluated to be “acceptable (this corresponds to an example)”, and the sample having the NO.sub.2 conversion rate of lower than 30% was evaluated to be “unacceptable (this corresponds to a comparative example).
[0080] 9. Evaluation Item (Particle Diameter of Cerium Dioxide)
[0081] The particle diameter of the cerium dioxide was calculated by image analysis. The prepared honeycomb structure (porous ceramic structural body) was enclosed in a resin and subjected to mirror surface polishing by using a diamond slurry and the like, and the product was used as an observation sample for the image analysis. This cross-sectional polished surface that had undergone the mirror surface polishing was observed under a scanning electron microscope at 10,000-fold magnification, whereby a reflection electron image photograph (microstructure image) of the porous ceramic structural body was obtained. The obtained reflection electron image photograph was subjected to binarization processing by using image analysis software (trade name: Image-Pro0.7), and adjusting the contrast so as to distinguish the area of cordierite from the area of cerium dioxide. By such binarization treatment, the profile of each cross-sectional area of cerium dioxide was determined, and the particle diameter of cerium dioxide was measured.
[0082] 10. Rate of Cerium Dioxide (CeO.sub.2) Particles Exposed on Pore Surfaces
[0083] The rate of the cerium dioxide particles was calculated by image analysis in a similar manner to that in the above-mentioned 9. In this evaluation, the cross-sectional polished surface that had undergone mirror surface polishing was observed under a scanning electron microscope at 750-fold magnification, whereby a reflection electron image photograph (microstructure image) of the porous ceramic structural body was obtained. The obtained image photograph was subjected to binarization processing by using similar image analysis software to that used in the above-mentioned 9, the profile of each cross-sectional area of cerium dioxide was determined, and the number of the cerium dioxide in the reflection electron image photograph was counted. Furthermore, the number of the cerium dioxide in contact with the pore surfaces was counted, and the rate (%) of the cerium dioxide particles disposed (exposed) on the pore surfaces, that is, the counted number of the cerium dioxide disposed on the pore surfaces/the number of the total cerium dioxide×100, was calculated. In the case when the catalytic amount of platinum was 5 g/L, the sample in which the rate of the cerium dioxide particles exposed on the pore surfaces was 10% or more was evaluated to be “fine”, the sample in which the rate was 3% or more and lower than 10% was evaluated to be “acceptable (this corresponds to an example)”, and the sample in which the rate was lower than 3% was evaluated to be “unacceptable (this corresponds to a comparative example) (except for Example 4).
[0084] 11. Consideration of Evaluation Results
[0085] As shown in Table 2, it was confirmed that Examples 1 to 5, which contained cerium dioxide, showed higher NO.sub.2 conversion rates than those of Comparative Examples 1 to 3, which were free from cerium dioxide (see
[0086] This result showed a possibility that higher catalyst performance is exerted at a higher rate of the exposed cerium dioxide on the pore surfaces. Furthermore, it was confirmed that a porous ceramic material of a silicon carbide component (Si/SiC) as in
[0087] Example 5 also has a similar effect to that of cordierite. In addition, it was confirmed that the effect of the present invention cannot be obtained even cerium dioxide is used simply as a catalyst as in Comparative Example 3, and thus it is necessary that the cerium dioxide is present in a state that it is contained in the structural body (incorporated state) as the constitutional component of the porous ceramic structural body, and a part of the cerium dioxide is exposed on the pore surfaces.
[0088] Although the preferable porous ceramic structural bodies of the present invention have been shown in the above-mentioned embodiments and Examples, but the present invention is not limited to these embodiments and Examples. For example, a porous ceramic structural body containing other metal oxide, which has a structural body containing cerium dioxide therein, wherein a part of the cerium dioxide has been substituted with a rare earth element or a transition metal element is also acceptable.
[0089] The porous ceramic structural body of the present invention can be preferably utilized as a catalyst carrier such as a catalyst carrier for purifying exhaust gas from automobiles.
DESCRIPTION OF REFERENCE NUMERALS
[0090] 1: honeycomb structure (porous ceramic honeycomb structure, porous ceramic structural body), 2a: one end face, 2b: other end face, 3: cell, 4: partition wall, 5: pore, 5a: pore surface, 6: particle, 7: catalyst particulate.