JPH09215928A - Deodorization catalyst for air conditioner for vehicle and its regenerating method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a deodorization catalyst for an air conditioner for vehicles by depositing a deodorization catalyst component for the air conditioner for vehicles which has a high deodorization treatment function without being affected by vapor in a gas to be treated even in highly humid environments and whose deodorization function is regenerated by heating regeneration treatment on a self-heat radiating type metal carrier which has a heat generating part to be heated to sufficiently high temperature for regeneration even by small and limited electric power from a battery built in a vehicle. SOLUTION: This deodorization catalyst for an air conditioner for vehicles consists of a self-heat radiating type metal carrier having a heat radiating part to radiate heat by electricity application, an adsorption layer formed on the carrier and consisting of a hydrophobic zeolite having silica/alumina ratio at least 100 and an amorphous mixture of zinc oxide and silicon dioxide, and catalytic components carrier on the layer and consisting of manganese dioxide and copper oxide. This regeneration method is to regenerate the deodorization catalyst for the air conditioner for vehicles.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a vehicle air conditioning deodorizing catalyst which can deodorize various odorous gases and harmful gases even in a high humidity environment and can be heated and regenerated by a small amount of electric power, and its heating and regenerating treatment. Regarding the method.

[0002]

2. Description of the Related Art In an air conditioner for a vehicle (hereinafter referred to as a car air conditioner), when the outside air is taken in by introducing the outside air, the outside air containing the exhaust gas and the offensive odor of a preceding vehicle is introduced into the vehicle interior. , Was giving offense to the occupants. In addition, the vehicle interior is contaminated by unpleasant odors emitted by the human body, odors caused by smoking, and the like.

Conventionally, an adsorbent such as activated carbon or zeolite has been widely used for removing these unpleasant odors, but it is uneconomical because it is almost disposable without being recycled and reused. In addition, a method of adsorbing and removing a bad odor by using an adsorption-type oxidative decomposition catalyst and heating it appropriately to regenerate a catalyst having a reduced adsorption capacity is widely used.

For example, in Japanese Patent Laid-Open No. 63-240923, an adsorbent such as activated carbon that adsorbs an odor in the air and a catalyst body such as a platinum alloy that decomposes the odor are held in a heat-resistant machine. The deodorizing filter is disclosed, "The odor in the air and the odor of tobacco are adsorbed and removed by an adsorbent such as activated carbon by passing through the deodorizing filter, and if the adsorbing ability is deteriorated after long-term use, the air cleaning is performed. Remove from the machine, put in an oven, etc.
Heat for 30 minutes. When the filter body is heated, the odor component adsorbed by the odor adsorbent is released, and at the same time, the odor component is decomposed by touching the catalyst. Therefore, since the filter is reactivated, it can be used again by incorporating it into the airframe. Is taught. However, the use of activated carbon as the adsorbent is dangerous because it may cause ignition when exposed to high temperatures during regeneration. Further, in order to regenerate, it is necessary to take it out of the machine, but in the case of a vehicle, it is difficult to take it out of the machine and carry out a regeneration process because the catalyst is installed in the passage of the car air conditioner.

Various heating and regenerating means for adsorption, oxidative decomposition and treatment capable of adsorbing, regenerating and decomposing odor have been proposed. Japanese Patent Publication No. 6-87951 discloses a method for regenerating a thermal decomposition catalyst using a defrosting heater for a refrigerator as a means for regenerating the thermal decomposition catalyst.

As a deodorizing device integrated with a heater,
For example, JP-A-7-155365, arsenate comprising a quartz or glass body incorporating an electrical resistor - capacitor - the molar ratio SiO ₂ / Al ₂ on the surface of the O ₃ is 8 or more zeolites, alumina and a noble metal Disclosed is a heating element provided with a deodorizing element containing. Further, although many deodorizing devices have been developed, in which a heater made of a conductor having a ceramic or metal as a base is separated or integrated into an adsorption oxidation decomposition catalyst layer (Japanese Patent Laid-Open No. 57-110311). 55-41
No. 862, JP-A-7-155365, JP-A-7-158876, etc.) all require a large amount of electric energy for heating to regenerate the catalyst. Further, a large number of self-heating metal honeycomb carriers have been proposed in order to collect particulates (fine particles) in exhaust gas discharged from automobiles, especially diesel engines. However, it is difficult to apply it to a vehicle in which the capacity of the power source is limited.

Further, it is expensive and uneconomical to use a platinum alloy as a catalyst.

On the other hand, Japanese Patent Publication No. 6-26671 discloses that
A catalyst comprising a transition metal selected from a non-noble metal or a noble metal consisting of chromium, nickel, iron, cobalt, copper, zinc and manganese and / or an oxide thereof in an amount of 20 to 80 wt. Si
O ₂ and 10~65wt%, 0.2~15wt the Al ₂ O ₃
%, MgO in an amount of 1 to 25 wt% is disclosed, and in a monolith type that does not cause an increase in pressure loss with time, it is possible to prevent a decrease in catalyst activity performance with time and always stabilize the performance. It is described as maintaining quality, and there is disclosure of ozone decomposing performance as well as CO removing performance.

Japanese Unexamined Patent Publication No. 7-16422 discloses ZnO.
Of 15 to 45% by weight, SiO ₂ of 20 to 50% by weight, manganese oxide of 10 to 50% by weight converted to MnO, copper oxide of 5 to 25% by weight of vanadium oxide converted to CuO. Disclosed is a deodorizing material comprising a molded body containing 3 to 15% by weight in terms of V ₂ O ₅ and capable of removing various odors generated in a toilet and a house. It is stated that it provides a highly efficient deodorant that can be obtained.

Japanese Unexamined Patent Publication No. 3-190805 discloses silver,
Disclosed is an antibacterial agent having a deodorizing performance, which is composed of an amorphous composite of an oxide of a metal having an antibacterial action selected from copper and zinc and silicon dioxide, and a metal having an antibacterial action is used as an oxide to form silicon dioxide. Amorphous composites have many advantages in terms of durability of antibacterial effect, stability of antibacterial substances, heat resistance, etc., and further, odorous gases such as ammonia, amines, hydrogen sulfide, and mercaptans. It was found that these compounds were chemically adsorbed by a coordinate bond with a metal, and it was described that the present invention was achieved. However, there is no mention of a method of regenerating a deodorizing member whose deodorizing performance is deteriorated by use and repeatedly using it.

[0011]

Heretofore, it has been known that activated carbon, activated alumina, silica gel, zeolite and the like are used as the adsorbent. As described above, various deodorizing materials have been proposed before the application, and deodorizing materials combining alumina, silica, manganese oxide, copper oxide and zinc oxide are also known before the application.

Activated carbon, which is a typical adsorbent, is hardly affected by moisture in the atmosphere and can sufficiently adsorb and remove harmful substances and malodorous substances even in a high humidity environment. However, when carrying out the heating regeneration treatment of the activated carbon whose adsorption capacity has been lowered by using it for deodorization treatment, there is a high risk of explosion and fire, and the activated carbon itself may burn. Further, it is difficult to recover the adsorption performance up to the initial adsorption performance by the heat regeneration treatment.

Further, in the passenger compartment of the vehicle, tar contained in odorous components such as acetaldehyde, acetic acid, propionic acid, methyl ethyl ketone, acetone, toluene, ammonia, etc. due to occupants and constituent members of the vehicle and cigarette smoke, Furthermore, exhaust gas from the vehicle that enters from outside the vehicle, such as SO
There is a need for a deodorizing material effective against malodorous gases such as x, NOx, hydrocarbons and / or harmful gases. Furthermore, in a high-humidity environment, conventional adsorbent deodorizers cannot cope with a large amount of water in the air and rapidly lose their adsorbing ability, failing to exert sufficient deodorizing effect. There is a demand for the development of a vehicle air conditioning deodorizing catalyst that can maintain a high deodorizing treatment capacity that is not easily affected by.

[0014]

DISCLOSURE OF THE INVENTION In order to deodorize malodorous gas and / or harmful gas at room temperature by adsorption and reaction, the present inventors have made effective use of reactions such as physical adsorption, chemical adsorption and switching. As a result of earnest research based on the finding that the catalyst used for the above is indispensable, it shows a high deodorizing treatment capacity without being affected by the moisture in the treated gas even in a high humidity environment, and it can be regenerated by heating. Succeeded in developing a deodorization catalyst for vehicle air conditioning that can restore deodorization performance, and carry it on a self-heating metal carrier that has a heating part that can raise the temperature to a sufficient regeneration temperature even with a small amount of electric power from a limited vehicle battery. As a result, we succeeded in developing a deodorizing catalyst for vehicle air conditioning.

That is, according to the present invention, (A) a self-heating type metal carrier having a heating portion which generates heat when energized, (B) (i) a silica / alumina ratio formed on the metal carrier is at least 100 or more. A hydrophobic zeolite and (ii) an adsorption layer composed of an amorphous composite of zinc oxide and silicon dioxide, and (C) a catalyst component composed of manganese dioxide and copper oxide supported thereon. The present invention relates to a characteristic deodorizing catalyst for vehicle air conditioning.

The present invention also provides (A) a self-heating metal carrier having a heating portion that generates heat when energized.
(B) an adsorption layer comprising (i) a hydrophobic zeolite having a silica / alumina ratio formed thereon of at least 100 or more, and (ii) an amorphous composite of zinc oxide and silicon dioxide; C) A deodorizing catalyst for vehicle air conditioning, which comprises a catalyst component composed of manganese dioxide and copper oxide supported on it, is applied to the heat generating part at a current as it is, periodically or irregularly, to the heat generating part. 5
The present invention relates to a method for regenerating a deodorizing catalyst for vehicle air conditioning, which comprises performing a heating regeneration treatment at a temperature of 00 ° C.

One component of the vehicle air-conditioning deodorizing catalyst of the present invention is a self-heating type metal carrier having a heat generating portion that generates heat when energized, and in particular, an insulating flat plate made of glass fiber or ceramic fiber. And a corrugated conductive slit-shaped metal corrugated sheet that can be heated to a sufficiently high reproduction temperature even with limited electric power from an on-vehicle battery, are laminated on each other, and are formed by zigzag folding or winding. Those that have As the conductive slit-shaped metal corrugated sheet, stainless steel material, chrome steel material, nickel-chrome steel material, Hastelloy alloy material or ferritic stainless steel material containing aluminum,
For example, a material having a high specific resistance value such as an iron-chromium-aluminum material such as Kanthal material is preferably thinned or formed into a foil. For example, as disclosed in Japanese Patent Laid-Open No. 7-208154, it is energized. A self-heating type metal carrier having a heating portion that generates heat is preferable because it can be heated by a small amount of electric power.

One example of manufacturing a metal carrier by winding is shown in FIG.
˜5 and FIGS. 6-8 will be described.

First, the first type will be described. The conductive slit-shaped metal corrugated plate 1 is welded to one cylindrical electrode 3 and the other end is welded to the electrode foil 4 (see FIG. 1).
In this way, an arbitrary number of conductive slit-shaped metal corrugated plates 1 are attached to the cylindrical electrode 3 so that the conductive slit-shaped metal corrugated plates 1 do not short-circuit with each other. Insert an insulator 2 such as a glass non-woven fabric between the two (see Fig. 2), wrap it and form it as shown in Fig. 3, then wrap it with a metal plate 5 and integrate 4 and 5 to form an outer electrode. To do. A partially enlarged view of the wound state thus obtained is shown in FIG. 4, and a photograph of the wound portion is shown in FIG.

In the other type, instead of the electrode foil 4 of the first type, an electrode plate 6 is projected in a direction perpendicular to the winding direction, and each conductive slit-shaped metal corrugated plate 1 is independent. In this way, it is possible to energize (see FIGS. 6 to 8).

Further, as an example of the structure of the metal carrier by means of the zigzag, a structure as shown in FIG. 9 can be exemplified.
A laminate of the conductive slit-shaped metal corrugated plate 1 and the insulator 2 may be folded and folded as shown in FIG. 9, and both ends of the conductive slit-shaped metal corrugated plate may be attached to the electrodes 3 and 4, respectively.

It is also possible to form an individual laminated body instead of the zigzag folding. In this case, each conductive slit-shaped metal corrugated plate can be connected to an independent electrode, or can be collectively connected to one electrode.

The electric resistance value of the metal carrier is inversely proportional to the cross-sectional area of the current path according to Ohm's law, and is proportional to the length of the current path. Therefore, the resistance value of the metal carrier can be increased by increasing the opening of the slit or by reducing the cross-sectional area in the direction of current flow such as by thinning the mesh portion. Further, by bending the metal carrier in a wave shape, the length of the current path can be increased and the resistance value can be further increased.

For example, a ferritic stainless steel plate made of Kawasaki Iron and Steel [R20-5S] having a thickness of 0.05 mm and a width of 10 mm.
R material: Fe-20Cr-5Al-REM (rare-metal) material] has a resistance value of about 3Ω per 1 m in length, but the stainless steel plate is subjected to expanded metallization (lath netting) to form a diagonal line. Length is 0.5mm, 1.0mm
The slit-shaped plate was provided with a rhombic slit, and the width of the conductive portion between the slits (the portion of the mesh line) was 0.16 mm. The width of the slit-shaped plate was 10 mm, and the resistance value per 1 m was about 21Ω.
That is, the slit-shaped plate has a resistance value about 7 times that of the stainless steel plate having no slit. The slit may have any shape such as a square or a circle, and may be formed by an appropriate method such as punching or etching in addition to expanding metal.

Furthermore, the weight of the metal carrier can be reduced by forming such slits (voids). By reducing the weight of the metal carrier, the heat capacity required to raise the temperature of the metal carrier can also be reduced, and sufficient heating regeneration can be performed even with an in-vehicle battery having a small electric capacity such as 12 V and 40 to 80 A. . By the way, the weight of the stainless steel plate (without slit) having a width of 10 mm and a length of 1 m is about 3.54 g.
However, the width of the slit-shaped plate that has been lath-netted is 10 m
The weight per m and the length of 1 m is about 1.78 g, which can be reduced to about 50% of the weight of the stainless steel plate having no slit, and the weight can be reduced. Along with this, the heat capacity of the heating element is also reduced at the same time (about 50% in the heating element part), and combined with the use of a material with a small heat capacity such as a plate (cloth) using glass fibers, the entire carrier is light and the heat capacity is small. It was possible to obtain a sufficiently high regeneration temperature and heating speed even with a small electric power such as an on-vehicle battery.

By forming the heat generating portion by a plurality of heat generating portions having different resistance values to form a metal carrier having regions having different temperature rising characteristics, only a desired portion is heated more than other portions. Since the characteristics can be improved, limited electric power can be effectively used. Further, by configuring so that each of the plurality of heat generating portions can be independently heated, each of the independent heat generating portions can be individually or separately controlled and heated. As a result, the whole can be heated and regenerated with a smaller amount of electric power, and a specific heat generating portion can be selected and heated, so that the deodorizing catalyst for vehicle air conditioning can be regenerated and heated more finely. That is, it takes a large amount of power or a long time to heat the entire catalyst at once, and it is difficult to heat the catalyst with an on-vehicle battery whose power supply capacity is limited, and it takes a long time to perform the heating regeneration process. The deodorizing function cannot be used for a long time because it becomes necessary. Therefore, it is possible to heat multiple heating units independently of each other, and to deodorize each independent heating unit individually or by dividing into multiple units and heating them sequentially or in an appropriate pattern. The function can be partially restored in a short time. Further, it is also possible to select and heat a specific heat generating portion (for example, a place where a large amount of air is passed), and the deodorizing catalyst for vehicle air conditioning can be heated and regenerated more finely.

Another component of the vehicle air-conditioning deodorizing catalyst of the present invention is hydrophobicity (water resistance) which constitutes an adsorption layer for malodorous substances.
It is an excellent zeolite.

The hydrophobic zeolite that can be used in the present invention is
Natural zeolites such as chabazite, mordenite, erionite, faujasite and clinoptilolite as well as zeolite A, zeolite X, zeolite Y, zeolite L, zeolite omega and ZSM-5.
It is preferable that the synthetic zeolite or the like is subjected to dealumina treatment so that the silica / alumina ratio becomes at least 100. Furthermore, silicalite, which is a crystalline silica containing almost no alumina, is most preferable. Silicalite has very low ion exchange capacity because it contains almost no alumina, and is hydrophobic and organophilic.

A typical silicalite has the following composition formula:

## EQU1 ## 1.0R ₂ O: 0 to 1.5M ₂ O: <0.05Al
₂ O ₃ : 40 to 70 SiO ₂ (In the formula, R represents a tetraethylammonium ion,
M represents an alkali metal cation. ).
The silicalite can be thermally decomposed by firing to remove organic cations. In the present invention, silicalite before firing or silicalite after firing can be used. As described above, silicalite contains almost no alumina, but actually alumina as an impurity contained in the raw material at the time of production may remain in silicalite which is the final product. Such small amounts of alumina do not affect the properties of the silicalite. Silicalite which can be used in the present invention has a silica / alumina ratio of at least 100, preferably 150 or more, particularly preferably 250 or more, and usually not more than 400. For the details of the production and properties of silicalite, see JP-A-54-72795, JP-B-56-40084, and Nature, Vol. 271, No. 5645, 512, issued on Feb. 9, 1978.
~ Silicalite, a novel hydrophobic crystalline silica molecular sieve on page 516.

Another component constituting the malodorous substance adsorbing layer of the vehicle air conditioning deodorizing catalyst of the present invention is an amorphous composite of zinc oxide and silicon dioxide (SiO ₂ .ZnO). As disclosed in JP-A-3-190805, it is possible to perform chemical synthesis by mixing amorphous hydrous silica and zinc oxide in an extremely fine state in an amorphous form. The adsorption layer is preferably prepared by preparing a uniform slurry of the hydrophobic zeolite and the amorphous composite (SiO ₂ .ZnO) and supporting it on a carrier by a method such as ordinary wash coating.

The amount of the hydrophobic zeolite loaded on the adsorption layer is 30 to 10 per 1 liter volume of the deodorizing catalyst for vehicle air conditioning.
It is 0 g, preferably 45 to 80 g. If the loading amount is less than 30 g, the adsorption effect of malodorous components is poor and 100 g
If it exceeds, the strength is not obtained and the adsorption layer is easily peeled off.

The amorphous composite (SiO ₂ .ZnO)
Loading of the adsorption layer of the vehicle air-conditioning deodorizing 1 liter catalyst volume per SiO ₂ · ZnO converted at 30 to 100 g, preferably 45～80G. When the supported amount is less than 30 g, the malodorous component adsorption effect is poor, and when the supported amount exceeds 100 g, when the slurry solution for supporting is prepared by mixing with the above-mentioned hydrophobic zeolite, not only the preparation becomes difficult, No strength is obtained and the adsorption layer is easily peeled off.

Another component of the vehicle air-conditioning deodorizing catalyst of the present invention is a catalyst component, which is composed of manganese dioxide and copper oxide. The catalyst component can be supported by a usual impregnation method. The manganese dioxide and the copper oxide may be supported as individual oxides, or may be supported in the form of a composite oxide. The supported amount of manganese dioxide is 30 to 100 g, preferably 40 to 80, in terms of MnO ₂ per 1 liter volume of the deodorizing catalyst for vehicle air conditioning.
g. If it is less than 30 g, the deodorizing effect cannot be expected, and 1
If the amount is more than 00 g, it is difficult to support, the strength is not obtained, and peeling easily occurs. The amount of copper oxide supported is 10 to 60 g, preferably 15 to 50 g, and more preferably 15 to 40 g in terms of CuO per 1 liter volume of the deodorizing catalyst for vehicle air conditioning.
g. If the amount is less than 10 g, the deodorizing effect cannot be expected and 60
If it exceeds g, it is difficult to carry it, and the strength is not obtained, and it is easily peeled off. The catalyst component is adsorbed and supported as fine particles on the amorphous composite (SiO ₂ .ZnO), and an adsorbent having high adsorption performance and oxidative decomposition performance can be easily prepared.

Acetaldehyde, which is one of the malodorous substances detected in the passenger compartment, itself has a low odor intensity, but after being adsorbed by the catalyst, it reacts and changes into acetic acid over time. Acetic acid has a high odor intensity and produces a strong malodor even in a small amount. However, acetic acid is effectively deodorized not only by physical adsorption in the adsorption layer but also by chemical adsorption by the catalyst component of the present invention.

By continuing the deodorizing treatment, the malodorous substance is physically adsorbed and / or chemically adsorbed, so that the deodorizing performance is deteriorated. A vehicle air conditioning deodorizing catalyst having a reduced deodorizing performance is used at 150 to 500 ° C., preferably 200 to 35 ° C.
The deodorizing performance can be restored by performing a heat regeneration treatment at a temperature of 0 ° C., more preferably 200 to 250 ° C. When the regeneration temperature is lower than 150 ° C, the odor is not sufficiently removed and the oxidative decomposition reaction is not sufficient. Furthermore, if the regeneration temperature is low, the oxidative decomposition reaction takes time, so an intermediate product is generated during the decomposition, and this substance may cause a new odor. On the other hand, if the temperature exceeds 500 ° C, not only the catalyst component undergoes a morphological change and the carrier is adversely affected,
This is disadvantageous because it requires extra electric energy and puts an unnecessary burden on the vehicle battery.

The deodorizing catalyst for vehicle air conditioning of the present invention is particularly effective as a deodorizing material for an automobile air cleaner because it can easily adsorb and remove SOx and NOx by the chemical adsorption action of the catalyst components.

[0037]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

1. Preparation of adsorption layer (1) Silicalite and amorphous composite (SiO ₂ ·
Adsorption layer made of ZnO 2.65 Kg of Snowtex (S
20% by weight as iO ₂ ) was added to 2.20 kg of ion-exchanged water to prepare a binder solution, and the binder solution had a silica / alumina ratio of 1.50 kg of 40.
Zero or more URAS PURAS IV-420 (silicalite) and Rasa Kogyo Co., Ltd. Shu Cleanse (amorphous composite of zinc oxide and silicon dioxide) were added while stirring with a propeller stirrer to obtain a solid content. Of 45.0% by weight (SiO ₂ : 6.8% by weight, silicalite: 19.1% by weight, SiO ₂ · ZnO: 19.1)
Wt%) 7.9 Kg was prepared.

Eight pairs of spirally wound conductive slit-shaped metal corrugated sheets made of corrugated ferritic stainless steel lath mesh with a separator made of glass tape interposed therebetween,
The above-mentioned slurry solution is sprinkled on a self-heating carrier (500 cells, diameter 75 mm, thickness 19 mm) manufactured by Nippon Denso Co., Ltd., which is provided with electrodes for applying a heating current to the center and outer circumference of the winding. After removing the excess slurry by blowing air, it was dried at a temperature of 150 ° C. for 3 hours. The dried carrier was calcined at a temperature of 380 ° C. for 1 hour to obtain 130 g of solid content (silicalite: 5
An adsorption carrier A coated with 5 g / liter and SiO ₂ .ZnO: 55 g / liter was prepared.

The conductive slit-shaped metal corrugated plate is made of chromium 18 to 24 wt% and aluminum 4.5 to 5.
5 wt%, rare earth element (REM) 0.1-0.2 wt
%, The balance is made of an alloy consisting of iron, and the plate thickness is 30
~ 150 μm, slits are generally diamond shaped (Fig. 1
0), slit width (a) 0.12 to 0.16 mm, slit length (b) 1.0 to 2.0 mm, slit spacing (c)
0.5 to 1.0 mm, and the corrugated plate has a pitch of 2.
The unevenness has a size of 6 mm and a height of 1.6 mm.

(2) Adsorption layer made of silicalite 4.0 kg of Snowtex (SiO)
20 wt% as ₂ ) was added to 2.75 Kg of ion-exchanged water to prepare a binder solution, and 4.6 Kg of PURAS IV-420 (silica) made by UOP having a silica / alumina ratio of 400 or more was added to the binder solution. Light)
While stirring with a propeller stirrer, the solid content is 4
11.35 kg of a 7.5 wt% slurry solution (SiO ₂ : 7.0 wt%, silicalite: 40.5 wt%) was prepared.

The above self-heating carrier manufactured by Nippon Denso Co., Ltd. was sprinkled with the above-mentioned slurry solution, and the excess slurry was blown with air to remove it, followed by drying at a temperature of 150 ° C. for 3 hours. Calcining the dried carrier at a temperature of 380 ° C. for 1 hour,
An adsorption carrier B coated with 120 g of solid content (containing 101 g / liter of silicalite) per liter of carrier was prepared.

(3) Amorphous composite (SiO ₂ .Zn
O) Adsorption layer 450g Snowtex (SiO
20% by weight as ₂ ) was added to 950 g of ion-exchanged water to prepare a binder solution, and 600 g of Rhua Kogyo Co., Ltd. Shucleanse (amorphous composite of zinc oxide and silicon dioxide) was added to this binder solution. Of the slurry solution having a solid content of 34.5% by weight (SiO ₂ : 4.5% by weight, SiO ₂
-ZnO: 30.0 wt%) 2000 g was prepared.

Similarly, this slurry solution was sprinkled on the above-mentioned self-heating carrier manufactured by Nippon Denso Co., Ltd., excess slurry was blown off to remove the slurry, and the carrier was dried at a temperature of 150 ° C. for 3 hours. The mixture was calcined at a temperature of ° C for 1 hour to prepare an adsorption carrier C coated with 70 g of a solid content [containing 68 g / l of an amorphous composite (SiO ₂ .ZnO)] per liter of the carrier.

(3) Adsorption layer composed of mordenite zeolite 450 g of Snowtex (SiO
20 wt% as ₂ ) was added to 950 g of ion-exchanged water to prepare a binder solution, and 600 g of silica / alumina ratio LZM-5 (mordenite zeolite) manufactured by UOP having a ratio of 11 was propeller-stirred in the binder solution. Add 34.5% by weight of solid content while stirring with a machine.
2000 g of a slurry solution of (SiO ₂ : 4.5% by weight, mordenite zeolite: 30.0% by weight) was prepared.

Similarly, this slurry solution was sprinkled on the above-mentioned self-heating type carrier manufactured by Nippon Denso Co., Ltd., excess slurry was blown to remove the slurry, and the carrier was dried at a temperature of 150 ° C. for 3 hours. The mixture was calcined at a temperature of ° C for 1 hour to prepare an adsorption carrier D coated with 80 g of solid content (containing 69 g / l of mordenite zeolite) per liter of the carrier.

2. Preparation of impregnation solution

(1) Manganese nitrate solution A manganese nitrate solution (containing 50% by weight as Mn (NO ₃ ) ₂ ) manufactured by Tanaka Chemical Co., containing 15.4% by weight in terms of Mn was used.

(2) Copper Nitrate Solution To 500 g of copper nitrate [Cu (NO ₃ ) ₂ .3H ₂ O] crystals, 354 g of ion-exchanged water was added and dissolved, and converted to Cu to obtain 1
A copper nitrate solution containing 5.4% by weight was prepared.

(3) Manganese nitrate / copper nitrate solution To 600 g of the above 15.4% manganese nitrate solution, 11
Manganese nitrate containing 7 g of copper nitrate [Cu (NO ₃ ) ₂ .3H ₂ O] crystals dissolved therein and containing 12.9% by weight in terms of Mn and 4.29% by weight in terms of Cu. A copper nitrate solution (Mn: Cu weight ratio = 3: 1) was prepared.

3. Preparation of catalyst

Example 1 The adsorption carrier A was immersed in a manganese nitrate / copper nitrate solution, taken out, and the excess impregnating solution was blown with air to remove it.
It is dried at a temperature of 150 ° C. for 3 hours, and the dried carrier is baked at a temperature of 380 ° C. for 1 hour while flowing air to remove the deodorant 1
A catalyst body A carrying 60 g of MnO ₂ .CuO per liter volume was prepared. The composition of catalyst A was 55 g of silicalite per 1 liter volume of the catalyst, 55 g of amorphous composite in terms of SiO ₂ · ZnO, 45 g of manganese dioxide in terms of MnO ₂ , and copper oxide in terms of CuO. It was 15 g.

Comparative Example 1 The same procedure as in Example 1 was carried out except that the adsorption carrier B was used as the carrier in Example 1, and the amount of catalyst was 5 per 1 liter volume of the catalyst body.
A catalyst body X carrying 5 g of MnO ₂ .CuO was prepared. The catalyst body X had a composition of 120 g of silicalite, 45 g of manganese dioxide in terms of MnO ₂ and 15 g of copper oxide in terms of CuO per liter volume of the catalyst body.

Comparative Example 2 A catalyst body Y carrying 55 g of MnO ₂ .CuO per 1 liter volume of the catalyst body was prepared in the same manner as in Example 1 except that the adsorption carrier C was used as the adsorption carrier. did. The composition of the catalyst body Y was such that the amorphous composite was 68 g in terms of SiO ₂ .ZnO, manganese dioxide was 45 g in terms of MnO ₂ , and the copper oxide was C in 1 liter volume of the catalyst body.
It was 15 g in terms of uO.

Comparative Example 3 A catalyst body Z carrying 55 g of MnO ₂ .CuO per liter volume of the catalyst body was prepared in the same manner as in Example 1 except that the adsorption carrier D was used as the adsorption carrier. did. The composition of the catalyst body Z is as follows: 69 g of mordenite zeolite and manganese dioxide are added per 1 liter volume of the catalyst body.
41 g in terms of MnO ₂ , copper oxide is 17 in terms of CuO
g.

4. Evaluation of deodorizing performance The sample was left overnight under saturated steam in a desiccator filled with water to absorb moisture sufficiently. It was confirmed that the sample, which had been left to absorb moisture overnight, stopped increasing in weight and showed a constant weight value, and saturated moisture absorption.

(1) Measurement of Amount of Adsorption of Ammonia Saturated moisture absorption treated sample (diameter 75 mm, thickness 19 mm)
(Volume: about 80 ml) is installed in a 16-liter glass reaction tank kept at a temperature of 25 ° C., and 9.6 ml of concentrated ammonia gas is injected into the reaction tank while rotating a fan for atmospheric circulation. The initial concentration of ammonia in the reaction tank was adjusted to 600 ppm / 16 liter. After standing for 30 minutes in this state, the concentration of ammonia was measured with a detector tube to prepare an adsorption isotherm at a temperature of 25 ° C.

The amount of ammonia adsorbed when the equilibrium concentration was 1 ppm was obtained from the adsorption isotherm, and the sample 8 when the equilibrium concentration was 1 ppm was used.
The adsorption amount (mg) of ammonia per 0 milliliter was calculated and shown in Table 1.

[0059]

[Table 1] ^* Nippon Denso Co., Ltd. self-heating carrier (500 cells, diameter 75 mm, thickness 19 mm)

[0060]

[Table 2]

As is clear from Tables 1 and 2, only the self-heating carrier (500 cells, diameter 75 mm, thickness 19 mm) manufactured by Nippon Denso Co., Ltd., which does not have an adsorption layer, or an amorphous composite (SiO 2) is used. _{In the} adsorption carrier C having an adsorption layer composed of only ₂ · ZnO) or the adsorption carrier D having an adsorption layer composed of mordenite zeolite, sufficient adsorption of ammonia is not carried out, and silicalite having hydrophobicity and amorphous The adsorbent carrier A having an adsorbent layer made of a composite of (SiO ₂ .ZnO) and the adsorbent layer adsorbent B having only hydrophobic silicalite have an increased amount of adsorbed ammonia due to physical adsorption. Recognize. In addition to physical adsorption, an increase in the amount of ammonia adsorbed due to chemisorption is observed in the catalyst bodies A, X, Y, and Z having a catalyst component in addition to the adsorption layer.

The catalyst body Z having an adsorption layer made of mordenite zeolite having no hydrophobicity is the same ammonia as the catalyst body A of the present invention having an adsorption layer made of silicalite having hydrophobicity, which is not subjected to the moisture absorption treatment. It has the adsorption ability of. However, as shown in Tables 1 and 2, the moisture-absorbed material shows only the amount of ammonia adsorbed by chemisorption by the catalyst component, and the adsorption layer made of mordenite zeolite absorbs moisture to improve the adsorption capacity of ammonia. , It can be seen that it has dropped significantly and is hardly functioning. That is, the catalyst body A of the present invention having an adsorption layer composed of silicalite having a hydrophobic property and an amorphous composite (SiO ₂ .ZnO) and a catalyst component composed of manganese dioxide and copper oxide has a high humidity and is harsh. It was proved to have excellent ammonia adsorption performance even under the conditions.

(2) Measurement of Adsorption of Methyl Ethyl Ketone The moisture-absorbed sample was placed in a 16-liter glass reaction tank kept at a temperature of 25 ° C., and a dimethyl ethyl ketone solution 6.5 was used while rotating a fan for atmospheric circulation. Microliter was injected into the reaction tank to adjust the initial concentration of methyl ethyl ketone in the reaction tank to 100 ppm / 16 liter. After standing in this state for 30 minutes to reach adsorption equilibrium, the concentration of methyl ethyl ketone was measured by a FID gas chromatography analyzer to prepare an adsorption isotherm at a temperature of 25 ° C. The adsorption amount of methyl ethyl ketone at the equilibrium concentration of 1 ppm was obtained from the adsorption isotherm, and the adsorption amount (mg) of methyl ethyl ketone per 80 ml of the sample at 1 ppm was calculated and shown in Tables 3 and 4.

[0064]

[Table 3] ^* Nippon Denso Co., Ltd. self-heating carrier (500 cells, diameter 75 mm, thickness 19 mm)

[0065]

[Table 4]

It is proved from Tables 3 and 4 that the adsorption carrier or the catalyst body having the adsorption layer made of silicalite having hydrophobicity has a high adsorption ability for methyl ethyl ketone.

(3) Measurement of adsorbed amount of acetic acid A sample subjected to saturated moisture absorption was placed in a 16-liter glass reaction tank kept at a temperature of 25 ° C., and 5 microliters of acetic acid was added while rotating a fan for circulating air. The initial concentration of acetic acid in the reaction tank was adjusted to 100 ppm / 16 liter by dropping it on a heater installed in the reaction tank and evaporating it. After leaving it for 30 minutes in this state, the acetic acid concentration was repeatedly measured many times up to the detection limit concentration (0.1 ppm) of the acetic acid detection tube, and the concentration below the detection limit concentration (0 p
Adsorption amount (mg) of acetic acid in pm) was determined and the results are shown in Tables 5 and 6.

[0068]

[Table 5] ^* Nippon Denso Co., Ltd. self-heating carrier (500 cells, diameter 75 mm, thickness 19 mm)

[0069]

[Table 6]

As is clear from Tables 5 and 6, the self-heating type carrier (500 cells, diameter 75 mm, thickness 19 mm) manufactured by Nippon Denso Co., Ltd., which does not have an adsorption layer, is of course the adsorption-treated hydrophobic substance. Even in the catalyst body Z having an adsorption layer made of mordenite zeolite having no property,
Almost no acetic acid odor can be removed. Further, as is clear from Tables 5 and 6, a catalyst body A having an amorphous complex of zinc oxide and silicon dioxide (SiO ₂ .ZnO) in the adsorption layer and supporting manganese dioxide as a catalyst component and It can be seen that the catalyst body Y has an excellent acetic acid adsorbing ability, and by supporting copper oxide as a catalyst component, the acetic acid adsorbing ability is improved. That is, a catalyst body A and a catalyst body Y of the present invention having a hydrophobic silicalite and an adsorption layer composed of an amorphous composite of zinc oxide and silicon dioxide and a catalyst component composed of manganese dioxide and copper oxide are ,
It has been proved to have excellent acetic acid adsorption performance even under severe conditions of high humidity.

5. Deodorization performance evaluation

Example 2 An example in which the deodorizing catalyst for vehicle air conditioning of the present invention is applied to a car air conditioner will be described. The outer peripheral surface of the catalyst body A of Example 1 having a diameter of 170 mm and a thickness of 57 mm was held by a heat insulating material, which was fixed in a case and mounted between a blower and a heat exchanger. A heating control sensor was attached. In the deodorization performance test using an actual machine, in order to prevent odors from being adsorbed by other components of the car air conditioner and apparently being highly evaluated for deodorization performance, a stainless steel test container having a volume equivalent to that of the passenger compartment. Was performed using. Set the temperature of the sample gas in the test container to 25
After adjusting the temperature and humidity to 50% and injecting acetaldehyde while rotating the circulation fan in the container to adjust the initial concentration of acetaldehyde in the container to 1.5 ppm, operate the blower of the car air conditioner, A sample gas was passed through the car air conditioner at a circulating air flow rate of about 165 m ³ / hour to measure the change with time of the acetaldehyde concentration in the test container, and the residual rate (%) of acetaldehyde in the container was calculated. Shown in.

[0073]

[Table 7]

As is clear from Table 7, it is understood that the catalytic body A exhibits excellent deodorizing performance. Moreover, when the removal rate of acetaldehyde when the sample gas passed through the catalyst body once was calculated from the residual rate of acetaldehyde in the test container, the removal rate of acetaldehyde was about 98%.
It was shown that the value of was high, and it was also applicable to the introduction of outside air from outside the vehicle. That is, an amorphous composite of hydrophobic zeolite, zinc oxide, and silicon dioxide (S
The deodorizing catalyst for vehicle air conditioning of the present invention in which manganese dioxide and copper oxide are supported as catalyst components in the adsorption layer composed of (iO ₂ .ZnO) has been proved to have excellent deodorizing performance by the actual equipment evaluation.

6. Regeneration test of catalyst body

Example 3 (1) Regeneration test of catalyst body after adsorption of ammonia A dimension of 57 m was measured by the same method as the method for measuring the adsorption amount of ammonia.
mx 70 mm x 20 mm (volume: about 80 ml)
Using the catalyst body A of Example 1 cut to the size of 1 as a sample, 9.6 ml of concentrated ammonia gas was injected into the reaction tank, left for 30 minutes to reach adsorption equilibrium, and then reacted with a detector tube. The ammonia concentration in the tank was measured. This operation was repeated to inject 96 ml of ammonia in total to create an adsorption isotherm at a temperature of 25 ° C. of the ammonia gas to determine the adsorption amount (mg) of ammonia per 80 ml of the sample. The sample that reached the adsorption equilibrium was placed in an electric furnace and heated and regenerated by changing the regeneration temperature and regeneration time. Similarly, the amount of adsorbed ammonia of the sample subjected to the regeneration treatment is obtained, and the regeneration rate (%) is obtained with the amount of adsorbed ammonia of the sample before regeneration being 100.
The reproduction time to reach 00% was obtained, and Table 8 shows the result.

[0077]

[Table 8]

As is clear from Table 8, it was proved that the catalyst body A of the present invention, which had adsorbed ammonia and had a reduced adsorption capacity, could be heated and regenerated at a temperature of 200 ° C. or higher. NOx was not detected in the gas discharged from the electric furnace.

Example 4 (2) Regeneration of catalyst body after adsorbing acetaldehyde As a sample, the catalyst body A of Example 1 was placed in a 16-liter glass reaction tank kept at a temperature of 25 ° C. While rotating the fan, 4 microliters of acetaldehyde solution was injected into the reaction tank, left for 15 minutes to reach adsorption equilibrium, and then the concentration of acetaldehyde was measured by a FID gas chromatography analyzer. After repeating this operation and injecting 56 microliters of acetaldehyde in total amount to prepare a sample that reached adsorption equilibrium, the sample was placed in an electric furnace in the same manner as in Example 2 and the regeneration temperature and regeneration time were changed to perform heat regeneration treatment. did. Similarly, the amount of acetaldehyde adsorbed on the regenerated sample was calculated, and the regeneration rate (%) was calculated with the amount of acetaldehyde adsorbed on the sample before regeneration being 100. The regeneration time at which the regeneration rate reached 100% at each temperature was calculated. Table 9 shows the results.

[0080]

[Table 9] As is clear from Table 9, it was proved that the catalyst A of the present invention, which adsorbed acetaldehyde and had a reduced adsorption ability, could be regenerated by heating at a temperature of 150 ° C. or higher.

Example 5 (3) Regeneration of catalyst body after adsorption of acetaldehyde by actual equipment A catalyst body similar to that of Example 2 in which acetaldehyde was saturated and adsorbed was placed in the stainless test container of Example 2 and the on-vehicle battery was installed. Using the catalyst body surface temperature of about 250 ℃
The temperature was raised to 10 minutes, and the temperature was maintained for about 10 minutes for regeneration treatment. The power consumption at this time was about 110 W. When the regenerated catalyst body was subjected to the acetaldehyde deodorizing performance evaluation test in the same manner as in Example 2, it showed the same excellent deodorizing performance as in the initial stage, and it is confirmed that it can be sufficiently heated and regenerated even by a vehicle battery with a small electric capacity. Was given.

Example 6 (4) Regeneration of catalyst body after adsorption of acetic acid After acetic acid was sufficiently adsorbed on the catalyst body A of Example 1 to reach adsorption equilibrium, temperature-programmed oxidation analysis (TPO FID gas chromatography analysis) was carried out. However, it was confirmed that acetic acid was oxidatively decomposed at 200 ° C to 250 ° C.

Example 7 (5) Regeneration of catalyst body after adsorption of tobacco smoke The catalyst body A of Example 1 was used as a sample and placed in a 16-liter glass reaction tank kept at a temperature of 25 ° C. Three cigarettes attached with were put into a reaction tank, and left for 1 hour while rotating a fan for circulating air. At this time, the weight of the sample was found to increase by about 0.8 g. 250 this sample
After regenerating at 30 ° C. for 30 minutes, the acetaldehyde adsorption performance was measured in the same manner as the acetaldehyde adsorption performance measurement method of Example 4, and at the same time, the weight change of the sample was measured. The above-mentioned cigarette smoke adsorption and sample regeneration operations are 2
The sample regenerated even after repeated 0 times did not show any increase in weight, and almost no deterioration in the acetaldehyde adsorption performance was observed. In addition, no tobacco odor was felt from the sample itself.

(Evaluation) As described above, by continuously performing the deodorizing treatment, the deodorizing performance for the vehicle is lowered because the malodorous substance is absorbed by the deodorizing catalyst for vehicle air conditioning of the present invention by physical adsorption or chemical adsorption. Catalyst, 150-50
It was proved that the heating and regeneration treatment at a temperature of 0 ° C. can restore the deodorizing performance, and the heating and regeneration treatment of the catalyst body having the reduced deodorizing performance can be performed.

[0085]

【effect】

1. Even in a high-humidity environment, a high deodorizing treatment capacity can be maintained for a long time. 2. The deodorizing ability can be regenerated many times by the heat regeneration treatment. 3. Ammonia, acetic acid each adsorption capacity, and ammonia, acetic acid, in each regeneration capacity of the vehicle air conditioning deodorizing catalyst after respectively adsorbing acetaldehyde, the vehicle air conditioning deodorizing catalyst of the present invention has excellent results in each case, Particularly, the adsorption performance of acetic acid, which has a strong bad odor, is significantly improved. On the other hand, those lacking the specific requirements for the adsorption layer or those lacking any of the catalyst components showed some defects in any of the adsorption capacity or the regeneration capacity. 4. Even if harmful components such as cigarette smoke and tar are adsorbed or adhered and the deodorizing ability is lowered, the deodorizing ability can be recovered by the heat regeneration treatment. 5. Since SOx and NOx can also be adsorbed and removed, it is effective as a catalyst body for automobile air cleaners. 6. Since the heat generating part of the vehicle air conditioning deodorizing catalyst is composed of a corrugated conductive slit-shaped corrugated plate,
It has a high electric resistance and can be heated to the required regeneration temperature by the on-vehicle battery.

[Brief description of drawings]

FIG. 1 is a perspective view showing an example of a connection mode between a conductive slit-shaped metal corrugated plate and an electrode used for producing a deodorizing catalyst for air conditioning of a wound type vehicle.

FIG. 2 is a perspective view of an intermediate product in the case of manufacturing the whole heating type of the deodorizing catalyst for air conditioning of a wound type vehicle.

FIG. 3 is a cross-sectional view of an entire heating type deodorizing catalyst for air conditioning of a wound type vehicle.

FIG. 4 is a photograph showing a fiber shape.

5 is a partially enlarged photograph of FIG.

FIG. 6 is another one of the connection modes of the conductive slit-shaped metal corrugated plate and the electrode used for the production of the deodorizing catalyst for the winding type vehicle air conditioning.
It is a perspective view showing an example.

FIG. 7 is a perspective view of an intermediate product when a partially heated type deodorizing catalyst for air conditioning of a wound type vehicle is manufactured.

FIG. 8 is a sectional view of a partially heated type deodorizing catalyst for air conditioning of a wound type vehicle.

FIG. 9 is a perspective view showing an example of a deodorizing catalyst for air conditioning of a zigzag folded vehicle.

FIG. 10 is a top view of the conductive slit-shaped metal corrugated plate before corrugation.

[Explanation of symbols]

 1 Conductive slit-shaped metal corrugated plate 2 Insulating flat plate (insulator) 3 Cylindrical electrode 4 Electrode (electrode foil) 5 Electrode (electrode plate) 6 Electrode plate

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location B01J 29/076 B01J 29/076 A 35/04 321 35/04 321A (72) Inventor Yasushi Yamazaki 1-1, Showa-machi, Kariya city, Aichi Prefecture, Nihon Denso Co., Ltd. (72) Inventor, Yukihisa Takeuchi 1-1, Showa-cho, Kariya city, Aichi prefecture, Nihon Denso Co., Ltd. (72) Inventor, Sakura Shin Hiratsuka city, Kanagawa prefecture 1212 Shinomiya Inside JGC Universal Co., Ltd.

Claims (11)

[Claims] 1. A self-heating metal carrier having (A) a heat-generating portion that generates heat when energized, (B) (i) a silica / alumina ratio formed thereon is at least 1.
An adsorption layer composed of a hydrophobic zeolite of at least 00 and (ii) an amorphous composite of zinc oxide and silicon dioxide,
And (C) a catalyst component composed of manganese dioxide and copper oxide supported thereon, a deodorizing catalyst for vehicle air conditioning. 2. The self-heating type metal carrier according to claim 1, wherein an insulating flat plate made of glass fiber or ceramic fiber and a corrugated conductive slit-shaped metal corrugated plate are laminated, zigzag or The deodorizing catalyst for vehicle air conditioning according to claim 1, which is constituted by winding. 3. The deodorizing catalyst for vehicle air conditioning according to claim 1 or 2, wherein the heat generating portion according to claim 1 is constituted by a corrugated conductive slit-shaped metal corrugated plate. 4. The deodorizing catalyst for vehicle air conditioning according to claim 1, 2 or 3, wherein the self-heating type metal carrier according to claim 1 has a plurality of heat generating portions. 5. The heating elements adjacent to each other in the heating section according to claim 4 are insulated from each other, and at least one electrode is divided into a number of pairs of flat plates and corrugated plates, and the heating elements are divided and energized. The deodorizing catalyst for vehicle air conditioning according to claim 1, which is capable of being heated. 6. The deodorizing catalyst for vehicle air conditioning according to claim 1, 2, 3, 4 or 5, wherein the hydrophobic zeolite is silicalite. 7. The deodorizing catalyst for vehicle air conditioning according to claim 1, wherein the amount of the hydrophobic zeolite supported is 30 to 100 g per liter volume of the deodorizing catalyst for vehicle air conditioning. 8. The amount of the amorphous composite of zinc oxide and silicon dioxide supported is 30 to 100 g in terms of SiO ₂ .ZnO conversion per 1 liter volume of the deodorizing catalyst for vehicle air conditioning. The deodorizing catalyst for vehicle air conditioning according to 4, 6, or 7. 9. The supported amount of manganese dioxide is 30 to 30 in terms of MnO ₂ per 1 liter volume of a deodorizing catalyst for vehicle air conditioning.
The deodorizing catalyst for vehicle air conditioning according to claim 1, 2, 3, 4, 5, 6, 7 or 8, which has a weight of 100 g. 10. The carried amount of the copper oxide is 10 to 60 g in terms of CuO per liter volume of the deodorizing catalyst for vehicle air conditioning.
Claims 1, 2, 3, 4, 5, 6, 7, 8 or 9
Deodorizing catalyst for vehicle air conditioning described. 11. The method of claim 1, 2, 3, 4, 5, 6, 7,
Using the deodorizing catalyst for vehicle air conditioning according to 8, 9, or 10,
During normal use, the odorous gas and / or harmful gas is adsorbed at room temperature, and a heating current is applied to the heat generating part at 150-500 ° C at the same place regularly or irregularly.
A method for regenerating a deodorizing catalyst for vehicle air-conditioning, which comprises performing heating regeneration treatment at the regeneration temperature of.