JP3420627B2 - Ozone decomposition catalyst paper and ozone decomposition catalyst - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ozone decomposition catalyst paper which is excellent in strength and is excellent in various processability, particularly corrugation processability, and a corrugated form of such ozone decomposition catalyst paper. The present invention relates to a shaped catalyst having properties useful as a processed ozone decomposition catalyst.

[0002]

2. Description of the Related Art Conventionally, ozone decomposition catalyst paper containing an ozone decomposition catalyst component cannot be manufactured. This is because the ozone decomposing component is generally an oxide and has a strong oxidizing action, and when they are mixed in the paper, there are problems such as combustion and ignition in the drying step of papermaking. In addition, although ceramic fibers as a main component to prevent combustion have excellent heat resistance, they are low in strength and often cause problems in molding processes such as corrugating and pleating. Therefore, increase the plate thickness. There is a need. Therefore, the thing which can be used for practical use was not obtained.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and has no problem in the papermaking of ozone decomposition catalyst paper, and is an ozone decomposition catalyst thin paper excellent in strength. Since it has excellent processability, particularly corrugation processability, a corrugated ozone decomposition catalyst with low pressure loss and high specific contact area can be obtained, and by heating it at 200 to 400 ° C. It is an object of the present invention to provide an ozone decomposing catalyst having a very high activity by further supporting such an ozone decomposing catalyst and an active component having an ozone decomposing activity. In particular, the invention has a thickness of 25 to 150 μm, preferably 5
Since it is a thin paper in the range of 0 to 100 μm and has sufficient strength for corrugating, the resulting corrugated structure can have a high porosity and therefore a sufficient pitch. It can be made small, and thus, when it is used as a catalyst, or when a catalyst is further supported on it and used as a catalyst in a catalytic gas reaction of ozone decomposition, it is possible to increase the contact area with gas, Moreover, at that time, it is an object to provide an ozone decomposition catalyst paper and a corrugated ozone decomposition catalyst that can reduce the pressure loss due to the gas flow.

[0004]

The ozone decomposition catalyst paper according to the present invention comprises (a) 95-60% by weight of manganese carbonate,
(B) Containing 5 to 40% by weight of pulp composed of cellulose fiber, polyolefin fiber or aromatic polyamide fiber
However, the thickness is 25 to 150 μm .
In the present invention, as the pulp, hemp, cotton, softwood,
Not only wood pulp in the usual sense consisting of cellulose fibers extracted from plants such as hardwood, but also an aggregate of pulp-like synthetic fibers consisting of polyolefin fibers or aromatic polyamide fibers, that is, containing synthetic pulp, preferably Indicates that the water level was beaten to a value of 400 cc or less measured by a method according to JIS P-8121.

Examples of the synthetic pulp composed of the above polyolefin fibers include synthetic pulp composed of fibers such as polyethylene and polypropylene.
As the synthetic pulp composed of aromatic polyamide fibers (aramid fibers), for example, synthetic pulp composed of Kevlar fibers (trademark of Jupon Corporation in the United States) is favorably used. Here, the aromatic polyamide fiber is generally an organic synthetic fiber containing an aromatic polyamide as a main component, such as poly-m-phenylene isophthalamide and poly-p-phenylene terephthalamide.

In the present invention, such wood pulp and synthetic pulp can be used alone or in combination of two or more kinds. Among the above, wood pulp is most preferably used. However, the combined use of wood pulp and synthetic pulp composed of aramid fibers is one of the preferred embodiments of the present invention. In the ozone decomposition catalyst paper according to the present invention, the pulp as described above, together with glass fiber, sepiolite, when flame retardancy is required,
In order to obtain a wet paper web, a stock solution containing inorganic fibers such as ceramic fibers and, if necessary, other fibrous fillers, reinforcing materials, additives, etc. can be obtained by paper making by a usual paper making method. The heat-resistant paper may contain 5 to 30% by weight.

According to the present invention, in ozone-decomposing paper,
When the content of pulp is too small, when forming a stock solution with a paper machine, formation of texture is not possible, the strength of wet and dry is too small, and the desired strength of thin paper The product cannot be obtained, and processing such as corrugation processing becomes difficult. In other words, by using a certain amount of pulp, it is possible to perform processing such as corrugation processing with good productivity. On the other hand, when the content of pulp is too large, the papermaking properties of the stock solution are improved, but the resulting ozone-decomposed paper is inferior in dimensional stability. When the ozone-decomposed paper is supported by a wet impregnation method, wrinkles may occur when the ozone-decomposed paper is dried, and the strength and shape retention are insufficient, and the target molded catalyst cannot be obtained. .

The manganese carbonate used in the present invention is obtained by adding ammonium bicarbonate or sodium bicarbonate to a manganese sulfate solution, manganese oxide is dissolved in ammonia carbide, and manganese carbonate or manganese carbonate obtained by passing steam through this is dissolved. Although manganese carbonate, which is a mineral product, can be used, alkali metals and alkaline earth metals exhibit a catalyst poisoning action, and those containing a large amount of these are not preferred. In addition to these, it is also possible to use a mixture of manganese carbonate and styrene, alumina adsorbing odorous components such as lower fatty acid alcohols, activated carbon, silica, etc. uniformly or physically by a precipitation method or the like. These manganese carbonates are contained in the obtained ozone-decomposed paper in an amount of 95 to 60% by weight. If it is 95% or more, a paper having sufficient strength cannot be obtained, and if it is 60% or less, sufficient ozone decomposition performance cannot be obtained.

In the present invention, the glass fiber optionally used is useful for preventing the expansion and contraction of pulp in the obtained ozone-decomposed paper, giving excellent dimensional stability and heat resistance. In the present invention, such glass fiber may be contained in the range of 5 to 10% by weight, if necessary. When the glass fiber content in the ozone-decomposed paper is too high, when making the stock solution,
Uniform formation cannot be achieved, and the desired thin paper-shaped shochu hot paper cannot be obtained. Further, since the obtained heat-resistant paper has too high air permeability, it is difficult to carry out an adhesion process such as a flute process in corrugation process or a pleating process. On the other hand, when the content of the glass fiber is too small, the expansion and contraction of the pulp cannot be suppressed in the resulting heat-resistant paper, the dimensional stability is deteriorated, and the heat resistance is also deteriorated.

Further, the ozone-decomposing paper according to the present invention may contain sepiolite. Sepiolite is a fibrous natural clay mineral whose main component is hydrous magnesium silicate. Fiber diameter is around 0.1 μm, fiber length is several tens of μm
To several mm, and the single fiber has a large number of pores of angstrom unit. Since sepiolite has a very small fiber diameter and the fibers are strongly intertwined with each other, the heat-resistant paper containing it is dense and strong even if it is a thin leaf, so it is excellent in moldability such as corrugating. Not only does it have excellent heat resistance. Furthermore, since sepiolite has a large number of pores due to its crystal structure, heat resistant paper containing sepiolite is excellent in carrying a catalyst and the like. Further, the ozone-decomposing paper according to the present invention may contain an inorganic short fibrous filler made of rock wool, wollastonite, ceramic fibers or potassium titanate.

Rockwool is a slag that contains silicic acid and calcium oxide as main components and other natural minerals that are melted at high temperature and then blown off by using centrifugal force to form fibers. Fiber diameter is several μm, fiber length is several tens μ
The range is from m to several mm. The fiber made of potassium titanate is an inorganic fiber obtained by subjecting titanium dioxide and, for example, potassium carbonate as a raw material to hydrothermal synthesis and the like, and the length thereof is usually several tens to several hundreds mm.

According to the present invention, such an inorganic short fibrous filler is mainly used when the content of pulp in the ozone-decomposing paper is reduced, that is, the heat-resistant strength of the obtained ozone-decomposing paper, that is, under the heating environment. It is used to reinforce the strength of the ozone decomposing paper and to keep the required strength of the ozone-decomposed paper even under the humidity condition in which the pulp strength decreases. Also,
According to the present invention, the strength-retaining effect can be further enhanced by forming an ozone-decomposed paper by corrugating or the like and then using an inorganic binder such as silica sol together.

Further, in the present invention, the strength of the ozone-decomposed paper obtained is reinforced, cracking during corrugation is prevented, and the strength required for heat-resistant paper is maintained even under the humidity condition in which pulp strength decreases. An organic short fiber reinforcing material may be included in order to retain the material. Here, the organic short fiber reinforcing material usually means an organic short fiber having a fiber diameter of about 3 to 30 μm and a fiber length of about 1 to 20 mm.

As such an organic short fiber reinforcing material,
For example, acrylic fiber, polyester fiber, polypropylene fiber, polyamide fiber, vinylon fiber and the like can be mentioned.

In addition to the above, the ozone-decomposing paper according to the present invention is, for example, an organic polymer such as polyacrylamide, melamine resin, polyacrylic acid ester, styrene-butadiene rubber, alumina sol or alumina sol in order to improve its physical properties. If necessary, an inorganic colloid such as silica sol may be contained.

The ozone decomposition catalyst paper according to the present invention can be suitably used as a catalyst itself, and can also be suitably used as a catalyst body as a corrugated or honeycomb structure according to a conventional method. . By heating such a catalyst body at 200 to 400 ° C., a more highly active catalyst body can be obtained. Furthermore, by supporting a catalyst component having excellent ozone decomposing activity, an extremely highly active ozone decomposing catalyst can be obtained.

[0017]

The present invention will be described below with reference to examples.
The present invention is not limited to these examples. In the following, as the glass fiber, fiber diameter 9
A chopped strand of μm and a fiber length of 3 mm was used.
The obtained heat-resistant paper was processed into a corrugated structure as follows. That is, using a gear with a mountain height of 1.2 mm and a pitch of 2.5 mm, using alumina sol (A-100 manufactured by Nissan Kagaku Co., Ltd.) as an adhesive agent, flute processing was performed, and then obtained. The flutes were cut into a predetermined size, and the same alumina sol as the above was used as an adhesive to perform a lamination process and form a corrugated structure.

Example 1 10 kg of pulp consisting of aramid fiber (KY-400S) manufactured by Daicel Chemical Co., Ltd., high-purity manganese carbonate 90 manufactured by Nippon Kagaku Co., Ltd.
Disperse a mixture of fibers consisting of kg in water with a pulper, transfer the obtained stock solution to a chest, paper it with a round rope part, dry the obtained wet paper with a cylindrical dryer, A heat resistant paper having a size of 90 μm was obtained. This manganese carbonate-containing paper was processed into a corrugated structure as described above.

Example 2 The corrugated catalyst obtained in Example 1 was further added to 200
By heating at ℃, 250 ℃, 300 ℃ for 3 hours, a corrugated catalyst was obtained.

Example 3 100 g of γ-MnO ₂ having a specific surface area of 127 m ² / g was homogeneously dispersed in 100 g of a 2 wt% alumina sol liquid, and the corrugated catalyst obtained in Example 1 was dipped in the slurry to make MnO in the corrugate. _2- Al ₂ O 3 is supported and 2
It was dried at 00 ° C to obtain a corrugated catalyst. At this time Mn
Loading amount of O ₂ -Al ₂ O ₃ was 29 g / 2l.

Example 4 A MnO ₂ —Al ₂ O ₃ -supporting corrugated catalyst was obtained in the same manner as in Example 3. However, the number of coats was twice. At this time, the carried amount was 66 g / l.

Example 5 The same procedure as in Example 1 was repeated except that 5 kg of pulp made of cellulose fiber, 5 kg of aramid fiber, 5 kg of glass fiber and 85 kg of manganese carbonate used in Example 1 were used as raw materials. Papermaking was carried out to obtain a manganese charcoal-containing paper having a thickness of 135 μm. This heat-resistant paper was processed into a corrugated structure as described above, and this corrugated catalyst was heated at 300 ° C. for 3 hours to obtain a corrugated catalyst.

Example 6 As raw materials, 5 kg of aramid fiber pulp, 5 kg of glass fiber, 5 kg of sepiolite, 2 kg of vinylon fiber (filler), and 83 k of manganese carbonate used in Example 1
Paper was made in the same manner as in Example 1 except that g was used to obtain a 120 μm thick manganese carbonate-containing paper. This paper was processed into a corrugated structure as described above, and 70 g of γ-MnO ₂ used in Example 3 and a specific surface area of 244 m ² were used.
/ G Ni ₂ O ₃ and 100% of 2.0% alumina sol liquid
It was immersed in a slurry that was homogeneously dispersed in, to carry the active ingredient, and thus a corrugated catalyst was obtained.

Example 7 In Example 1, 5 k of pulp made of aramid fiber was used.
A corrugated catalyst was obtained in the same manner as in Example 1 except that the amount of high-purity manganese carbonate manufactured by Nippon Kagaku Co., Ltd. was 95 kg. Further, this was heated at 300 ° C. for 3 hours to obtain a corrugated catalyst.

Example 8 In Example 1, the pulp containing aramid fiber was
A corrugated catalyst was obtained in the same manner as in Example 1 except that the amount of high-purity manganese carbonate manufactured by Nippon Kagaku Co., Ltd. was 85 kg.

Example 9 In Example 1, the pulp made of aramid fiber was changed to 25
Corrugated catalyst was obtained in the same manner as in Example 1 except that the amount of high-purity manganese carbonate manufactured by Nippon Kagaku Co., Ltd. was 75 kg.

Example 10 Manganese carbonate-containing papers having various thicknesses were obtained in the same manner as in Example 1. A corrugated catalyst having a height of 20 mm was obtained from each of these heat-resistant papers as described above. The pressure loss when air was passed through the corrugated catalyst at a speed of 2 m / sec was determined. The results are shown in Table 1.

Comparative Example 1 A paper was prepared in the same manner as in Example 1 except that 10 kg of pulp made of cellulose fiber and 90 kg of ceramic fiber (Fineflex 1300 manufactured by Nichias Co., Ltd.) were used as raw materials, but it was inferior in corrugating. So thickness 1
A 50 μm ceramic paper was obtained. This paper was processed into a corrugated structure as described above, and an active component was carried in the same manner as in Example 3 to obtain a corrugated catalyst. At this time, the amount of MnO ₂ —Al ₂ O ₃ supported was 61 g / l.
Met.

The catalysts obtained in Examples 1 to 9 and Comparative Example 1 were subjected to a catalyst activity test under the following reaction conditions using a test apparatus having a flow sheet shown in FIG.
The ozone decomposition rate was calculated after 10 hours and 100 hours. In the figure, (1) is an ozone generator,
Ozone having an appropriate concentration is generated from the air introduced therein, and this ozone-containing air is guided to the catalyst layer (2). The ozone decomposition rate (%) is calculated by the following equation from the values at the inlet and outlet of the catalyst layer measured by the ozone analyzer in (3). (Reaction conditions) Area velocity: 50 m ³ / m ² · hr Inlet ozone concentration: 2 ppm Reaction temperature: 28 ° C. Relative humidity: 80% The test results are shown in Table 2.

As is clear from the above table, Examples 1-9
Each of the catalysts obtained in Example 1 has higher durability than the catalyst obtained in Comparative Example 1.

[0031]

The ozone decomposition catalyst according to the present invention has an excellent effect of efficiently removing ozone.

[0032]

[Brief description of drawings]

FIG. 1 is a flow sheet of a catalyst activity test.

[Explanation of symbols]

(1) …………………… Ozone generator (2) ……………………… Catalyst layer (3) ………………… Ozone analyzer

[Table 1]

[Table 2]

─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-5-317717 (JP, A) JP-A-4-104840 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) B01J 21/00-37/36 B01D 53/86 D21H 27/00

Claims (6)

(57) [Claims] 1. (a) 95-60% by weight of manganese carbonate
(B) Containing 5 to 40% by weight of pulp composed of cellulose fiber, polyolefin fiber or aromatic polyamide fiber
The ozone decomposition catalyst paper is characterized by having a thickness of 25 to 150 μm . 2. (a) 95-60% by weight of manganese carbonate
(B) By heat- treating a paper containing 5 to 40% by weight of pulp composed of cellulose fibers, polyolefin fibers or aromatic polyamide fibers at 200 to 400 ° C.
The obtained ozone decomposition catalyst paper is characterized by having a thickness of 25 to 150 μm . 3. (a) 95-60% by weight of manganese carbonate
(B) contains 5 to 40% by weight of pulp composed of cellulose fiber, polyolefin fiber or aromatic polyamide fiber
An ozone decomposition catalyst formed by forming an ozone decomposition catalyst paper having a thickness of 25 to 150 μm in a corrugated structure. 4. (a) 95-60% by weight of manganese carbonate
(B) contains 5 to 40% by weight of pulp composed of cellulose fiber, polyolefin fiber or aromatic polyamide fiber
An ozone decomposition catalyst, characterized in that an ozone decomposition catalyst paper having a thickness of 25 to 150 μm is formed on a corrugated catalyst body and further heat-treated at 200 to 400 ° C. 5. (a) 95-60% by weight of manganese carbonate
(B) contains 5 to 40% by weight of pulp composed of cellulose fiber, polyolefin fiber or aromatic polyamide fiber
An ozone decomposition catalyst characterized by comprising a corrugated structure on which ozone decomposition catalyst paper having a thickness of 25 to 150 μm is formed, and further supporting a catalyst component having ozone decomposing ability. 6. (a) 95-60% by weight of manganese carbonate
(B) Containing 5 to 40% by weight of pulp composed of cellulose fiber, polyolefin fiber or aromatic polyamide fiber
200-400 ° C. obtained by forming an ozone decomposition catalyst paper having a thickness of 25-150 μm on a corrugated catalyst body
An ozone decomposing catalyst, which is heat-treated at 1, and further carries a catalyst component having ozone decomposing ability.