JP2925122B2 - Method for producing honeycomb-shaped ceramic catalyst support - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a high-performance honeycomb-shaped ceramic catalyst carrier having a very large surface area per unit volume as a catalyst carrier, and evenly supporting a large amount of catalyst per unit volume without separation or scattering of catalyst particles. It concerns the manufacturing method.

[0002]

2. Description of the Related Art A small amount of organic fibers and a binder are added to a ceramic fiber to form a honeycomb-shaped laminate with paper. Japanese Patent Publication No. 59-15028 discloses a method of firing a molded product and burning off the organic fibers and organic binder in the paper to obtain a catalyst carrier.

[0003]

When a catalyst such as titania or zeolite is impregnated and fixed in the form of a sol or the like on a catalyst carrier obtained by the above method, silica gel is already impregnated and fixed on paper or a molded product thereof. Therefore, when the catalyst particles are impregnated and supported on this carrier, it is extremely difficult for the catalyst particles to penetrate into the interstices of the fibers, and most of the catalyst particles only adhere to the surface of the paper. It is difficult to support the catalyst, and defects such as desorption, separation, and carryover of the catalyst due to the flow of the processing fluid during use cannot be avoided.

According to the present invention, the catalytic activity is improved by further increasing the amount of the catalyst carried on the above-mentioned catalyst carrier, and even when a high-temperature or high-speed fluid is treated, the catalyst is desorbed, peeled off or carried over from the carrier. An object of the present invention is to obtain a high-performance catalyst carrier that does not have a possibility of causing the catalyst carrier.

[0005]

SUMMARY OF THE INVENTION According to the present invention, a ceramic fiber paper plane paper and a corrugated paper formed by using an organic or inorganic binder and containing ceramic fibers as a main component are bonded with an adhesive. Obtain a single-sided molded body, bond and laminate the single-sided molded body with an adhesive to form a honeycomb-shaped block, and bake the block with hot air having a reduced oxygen content to be included in the paper and the adhesive. After the organic component is incinerated to make it porous, the dispersion of the catalyst particles is impregnated to fix a large amount of the catalyst particles in the interstices and the surface of the fiber of the paper. By uniformly impregnating the dispersion of the inorganic binder into the gaps between the catalyst particles and the ceramic fibers and drying, the bonding strength between the fibers of the paper and the catalyst particles is increased. Is obtained desorption or stripping, or performance of the catalyst carrier that can withstand long-term use not occur carryover associated therewith catalyst particles even in the case of processing the speed of the fluid.

[0006]

EXAMPLE 1 The composition was composed of 85% by weight of ceramic fiber, 8% by weight of pulp and 7% by weight of organic binder, and had a thickness of 0.1%.
Wavelength 6.3 mm, wave height 3.5 m using ceramics paper formed to 22 mm, apparent specific gravity 0.5 g / cm ³
m, corrugated paper 1, 50% polyvinyl acetate emulsion with a solid content of 45%, silica sol 30 with a solid content of 20%
%, Catalyst particles such as titanium oxide (particle diameter 5 μ or less) 2
A single-sided molded article as shown in FIG. 2 was formed by adhering to the flat paper 2 using an adhesive having a composition of 0%, and the single-sided molded article was mixed with polyvinyl acetate, silica sol and catalyst particles in the same manner as described above. Lamination is performed using the agent to obtain the block shown in FIG. The bulk specific gravity of this block is about 75 kg / m ³ . Next, the block is placed in a firing furnace and the oxygen content is 10% or less, and the temperature is 65%.
0 ° C., flow rate 1.5 m / sec. Is passed through the small through-holes of the honeycomb and fired for 5 hours. Thereby, the bulk specific gravity of the block becomes about 61 kg / m ³ . Next, the block was immersed in a suspension containing about 30% of anatase type titanium oxide having a particle diameter of 5 μm or less for several minutes, and then heated at about 120 ° C. with hot air for about 60 minutes.
Dry for minutes. The bulk specific gravity of the block at this time is 153 kg
/ ^{M 3.} This was further immersed in a silica sol containing 20% silica having a particle diameter of 10 to 20 μm for several minutes,
It is dried by hot air of 00 ° C. to obtain a honeycomb-shaped ceramic catalyst carrier. The bulk specific gravity of this catalyst carrier is 179 kg / m
^{I got 3} .

[0007]

EXAMPLE 2 The composition was composed of 85% by weight of ceramic fibers, 8% by weight of pulp, and 7% by weight of a mixed organic and inorganic binder. The thickness was 0.22 mm, and the apparent specific gravity was 0.5 g / cm.
3.4m wavelength using ceramics paper made in ³
m, corrugated paper 1 having a wave height of 1.7 mm, adhered to flat paper 2 using an adhesive composed of 60% polyvinyl acetate emulsion having a solid content of 45%, and 40% silica sol having a solid content of 20%. The single-wave molded body shown in FIG. 2 is formed, and the single-wave molded body is laminated using an adhesive obtained by mixing an organic type and an inorganic type as described above to obtain a block shown in FIG. Bulk specific gravity of the block is about 154 kg / ^{m 3.} Next, the block is placed in a firing furnace and fired for 5 hours with hot air of 650 ° C. at an oxygen content of 10% or less. Thereby, the bulk specific gravity of the block becomes about 125 kg / m ³ . Next, the block is immersed in a suspension in which 40% of anatase-type titanium oxide having a particle size of 3 to 5 μm is dispersed in 60% of silica sol (solid content: 20%) having a particle size of 10 to 20 μm, and then heated at about 120 ° C. For about 30 minutes to obtain a honeycomb-shaped ceramic catalyst carrier. The bulk specific gravity of the obtained catalyst support was 360 kg / m ³ .

[0008]

EXAMPLE 3 The composition was composed of 85% by weight of ceramic fiber, 8% by weight of pulp and 7% by weight of organic binder, and had a thickness of 0.1%.
Using a ceramics paper formed to 40 mm, apparent specific gravity 0.45 g / cm ³ , wavelength 6.3 mm, wave height 3.5
mm, corrugated paper 1 mm, polyvinyl acetate emulsion 50% solids 50%, silica sol 30 solids 20%
%, Catalyst particles such as zeolite emulsion 20%
FIG.
A single-sided molded article as shown in FIG. 1 is formed, and the single-sided molded article is laminated using an adhesive obtained by mixing polyvinyl acetate, silica sol and catalyst particles such as zeolite in the same manner as described above to obtain a block shown in FIG. The bulk specific gravity of this block is about 110 kg / m ³
It is. Next, this block was placed in a firing furnace and the oxygen content was 10
%, A temperature of 650 ° C., and a flow rate of 1.5 m / sec. Is passed through the small through-holes of the honeycomb and fired for 5 hours. Thereby, the bulk specific gravity of the block becomes about 91 kg / m ³ . Next, the block is immersed in a suspension containing about 30% of zeolite having a particle diameter of 5 μm or less for several minutes, and then dried with hot air at about 120 ° C. for about 60 minutes. The bulk specific gravity of the block at this time is 233.
kg / m ³ . Further, this is immersed in a silica sol containing 20% of silica having a particle diameter of 10 to 20 μm for several minutes, and dried by hot air at a temperature of 300 ° C. to obtain a honeycomb-shaped ceramic catalyst carrier. The bulk density of this catalyst carrier is 268 kg
Atsuta in / ^{m 3.}

[0009]

Example 4 A composition of 85% by weight of ceramic fiber, 8% by weight of pulp, 7% by weight of a mixed binder of organic and inorganic substances, thickness 0.40mm, apparent specific gravity 0.45kg
/ Cm ³ was formed into a corrugated paper 1 having a wavelength of 6.3 mm and a wave height of 3.5 mm using ceramic paper, 60% of a polyvinyl acetate emulsion having a solid content of 45%, and 40% of a silica sol having a solid content of 20%. A single-sided molded article as shown in FIG.
The one-sided molded body is laminated by using an adhesive in which an organic type and an inorganic type are mixed in the same manner as described above to obtain a block shown in FIG. The bulk specific gravity of this block is about 113 kg / m ³ . Next, the block is placed in a firing furnace and the oxygen content is 10% or less, and the temperature is 65%.
0 ° C., flow rate 1.5 m / sec. For 5 hours. Thereby, the bulk specific gravity of the block is about 93 kg / m ³
become. Next, 40% by weight of zeolite having a particle size of 3 to 5 μm
Is a silica sol 6 having a particle size of 10-20 μm and a solid content of 20%.
The block is immersed in a suspension of 0% by weight for several minutes and then dried with hot air at about 120 ° C. for 30 minutes to obtain a honeycomb-shaped ceramic catalyst carrier. The bulk specific gravity of the obtained catalyst support was 267 kg / m ³ .

[0010]

According to the present invention, a honeycomb-shaped ceramic catalyst carrier carrying a large amount of a catalyst is used as a honeycomb-shaped catalyst for fluid treatment by further impregnating and adding a catalyst component and the like, if necessary.

[0011]

Since the present invention has the above-described structure, after forming a honeycomb-shaped block from ceramic fiber paper,
Prior to impregnating the dispersion of catalyst particles, hot air with reduced oxygen content was passed through the small pores of the honeycomb and fired, so that all organic components contained in the ceramic fiber paper and the laminating adhesive were decomposed and burned Or it is about 0.
Atsuta ceramics fiber paper with 5 g / cm ³ order of a bulk specific gravity of lower bulk density in a connexion porosity of about 0.3 to 0.5 g / cm ³ is further increased, a large amount of the catalyst particles or the fired block About 250% of the catalyst particles based on the weight of the catalyst, and all the organic components adhering to the block are removed, so that the adhesion of the catalyst particles is good. Since the inorganic binder such as alumina is impregnated in the form of a sol, the fine particles of the inorganic binder easily penetrate into the fibers of the ceramic fiber paper already supporting the catalyst particles and the gaps between the catalyst particles, and the catalyst particles with respect to the ceramic fiber paper. The catalyst catalyst carrier thus obtained is capable of separating or separating catalyst particles even when processing a high-speed fluid, and is scattered by carry-over. And is made of only non-combustible inorganic materials, so it is chemically stable without ignition or deterioration even at high temperatures, has very low pressure loss during fluid processing, and is resistant to mechanical external forces. Sufficiently durable, can be used semi-permanently as long as the performance of the supported catalyst does not change, and has the effect that it can be manufactured simply and reliably at a low cost without the need for expensive equipment or special technology. Things.

Further, when the thickness of the ceramic fiber paper is extremely reduced, the paper is apt to be broken during the formation of the single-wave molded article, and it is difficult to treat the satisfactory single-wave molded article and the honeycomb-shaped block. When the thickness is extremely large, it becomes difficult to form corrugated paper. However, in the present invention, since ceramic fiber paper having a thickness in the range of 0.1 to 0.4 mm is used, there is a problem in forming corrugated paper and treating honeycomb blocks. It has the effect of being able to work without.

Further, when an organic and inorganic catalyst particles are mixed and used as an adhesive for forming the one-sided molded article and / or as an adhesive for laminating the one-sided molded article, forming the one-sided molded article In addition, when laminating, the organic adhesive exhibits the initial adhesive strength, and after firing to remove the organic substances, the inorganic catalyst particles exhibit the adhesive strength together with the solid content of the inorganic binder such as silica sol, alumina sol and contribute to the reinforcement of the catalyst carrier. Can be done.

[Brief description of the drawings]

FIG. 1 is a perspective view showing an example of a block and a honeycomb-shaped ceramic catalyst carrier.

FIG. 2 is a perspective view showing a half-wave molded body.

[Explanation of symbols]

 1 Corrugated paper 2 Flat paper

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) B01J 35/04 B01J 35/06 B28B 1/00 B28B 1/52

Claims (4)

(57) [Claims] (1) ceramic fiber, pulp, organic or
Form a sheet made of inorganic binder into a half-wave molded body
Then, the single-sided molded body is laminated to form a honeycomb-shaped block.
Hot air with reduced oxygen content
Calcining the block through the pores, a dispersion of catalyst particles
Impregnated and dried to make the catalyst particles of the block of ceramic
After fixing between the fibers and on the sheet surface, the silica sol
Or impregnated and dried with a dispersion of an inorganic binder such as alumina sol
Of a honeycomb-shaped ceramic catalyst carrier
Manufacturing method. 2. A pulp 2 comprising 60 to 93% of ceramic fibers.
0-3%, organic or inorganic binder 20-4%
The thickness 0.1mm~0.4mm consists composition, molding the sheet forming the paper so as to be less apparent specific gravity of about 0.5 g / cm ³ to half-wave shaped body, honeycomb by laminating the half-wave shaped body the Jo block is formed, the hot air of reduced 400 to 750 ° C. the oxygen content was fired through the small hole of said block, ceramics impregnated with a dispersion of catalyst particles dried catalyst particles said block A method for producing a honeycomb-shaped ceramic catalyst carrier, comprising fixing a fiber between the fibers and the surface of paper, further impregnating a dispersion of an inorganic binder such as silica sol or alumina sol, and drying. 3. A pulp having a ceramic fiber content of 60 to 93%.
0-3%, organic or inorganic binder 20-4%
A paper formed to have a composition of 0.1 mm to 0.4 mm in thickness and an apparent specific gravity of about 0.5 to 0.25 g / cm ³ is formed into a half-wave molded body, and the half-wave molded body is laminated. To form a honeycomb-like block and reduce the oxygen content from 400 to 750.
C. hot air is passed through the small pores of the block and fired, impregnated with a mixed dispersion of catalyst particles and an inorganic binder such as silica sol or alumina sol, and dried to reduce the catalyst particles to the ceramic fibers of the block. A method for producing a honeycomb-shaped ceramic catalyst carrier, wherein the carrier is fixed to a gap and to the surface of paper. Organic as an adhesive when laminating the adhesive and or the half-wave shaped body when molding the 4. A half-wave shaped body
The method for producing a honeycomb-shaped ceramic catalyst carrier according to any one of claims 1 to 3, wherein an adhesive obtained by mixing a porous adhesive and inorganic catalyst particles is used.