JP2002333266A - Refrigerator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To maintain freshness of fruit and vegetable for a long period by improving removing performance of an ageing acceleration substance in a remov ing unit for removing a substance for accelerating ageing of the fruit and vegeta ble such as ethylene generated in a vegetable chamber by using a photocatalyst. SOLUTION: The photocatalyst 11, a white color adsorber 28, a removing element carrying a palladium-impregnated activated charcoal 29, and a light source 24 are built on the same hardware 27. Thus, even when the photocatalyst 11 does not function at the time of deenergizing the light source 24, removal of the ageing accelerating substance such as the ethylene or the like existing in the vegetable chamber 5 can be continuously removed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for removing a substance which promotes aging of fruits and vegetables using a photocatalyst and a palladium catalyst simultaneously, and a refrigerator provided with the apparatus.

[0002]

2. Description of the Related Art In recent years, refrigerators are not limited to simply cooling and storing foods, but diversifying the cooling temperature range, increasing the humidity inside the refrigerator, deodorizing, antibacterial, and losing nutrients (such as vitamins) in food. Various functions such as suppression are being studied, and it is expected that the functions required for refrigerators will increase in the future.

Most of the current refrigerators are equipped with an independent vegetable room, and by keeping the temperature and humidity environment suitable for the fruits and vegetables to be stored, the fruits and vegetables can be stored in a fresh state for a certain period of time. is there.

On the other hand, stored fruits and vegetables such as vegetables and fruits are known to deteriorate in freshness and quality due to ethylene (mature / aging hormone) generated by themselves and ethanol, acetaldehyde and the like (physiologically impaired substances). ing. Ethylene is also called mature or aging hormone,
It is a substance that significantly enhances the growth of fruits and vegetables and lowers freshness, for example, by increasing respiratory action, decomposing chlorophyll and accelerating softening of fruits. Ethanol and acetaldehyde are also volatile components produced by fruits and vegetables, and these components themselves are off-flavor components that not only impair the quality, but also cause physiological disorders such as internal browning of apples and deterioration of the appearance of kabos. .

[0005] Therefore, in order to maintain the freshness of the fruits and vegetables stored in the vegetable room for a longer period, not only the temperature and humidity environment is adjusted but also the aging promoting substance of the fruits and vegetables is removed and the air quality environment is adjusted. There is a need.

As a conventional refrigerator having a function of removing an aging promoting substance, there is one disclosed in Japanese Patent Application Laid-Open No. 7-270045.

Hereinafter, the conventional refrigerator will be described with reference to the drawings.

FIG. 16 is a vertical sectional view showing a vegetable room of a conventional refrigerator. In FIG. 16, reference numeral 1 denotes a refrigerator main body, which comprises a heat insulating box 2. The inside of the heat-insulating box 2 is vertically divided into a plurality of parts by a partition wall 3 having heat-insulating properties, and a plurality of storage chambers are formed in the heat-insulating box 2. In this case, 4 is a freezing room, and 5 is a vegetable room for storing vegetables, fruits and the like.

Reference numeral 6 denotes a cool air circulation path, and cool air cooled by a known refrigeration cycle incorporated in the main body 1 is supplied to the vegetable compartment 5 through the cool air circulation path 6. Reference numeral 7 denotes an opening / closing door of the vegetable compartment 5, which can take in and out vegetables and fruits stored in a storage container 8 in the vegetable compartment 5.

Reference numeral 9 denotes a cover for covering the upper opening of the storage container 8 of the vegetable compartment 5. An opening is provided at a substantially central portion of the cover 9, and the cover 9 covers the opening to form a moisture-permeable member. The member 10 is incorporated. The moisture permeable member 10 is formed in a rectangular thin plate shape from, for example, plastic, and has a large number of through holes formed in the plate surface. The moisture permeable member 10 controls the flow of water vapor through a large number of through holes, thereby adjusting the humidity in the storage container 8.

The moisture permeable member 10 has a photocatalyst 11 made of a metal oxide such as titanium dioxide or zinc oxide.
Are provided integrally. When titanium dioxide is used as the photocatalyst 11, the photocatalyst 11 has a wavelength of 380.
Under irradiation of ultraviolet light of nm or less, holes are generated on the surface,
The holes react with the water adsorbed on the surface of the photocatalyst 11 to generate radical OH (hydroxyl radical) having strong oxidative decomposition power. This radical OH breaks the molecular bond of organic matter, and also oxidizes plant aging accelerators such as ethylene and acetaldehyde released from vegetables and fruits by photocatalyst, and eventually to water and carbon dioxide. Can be disassembled.

Further, a light source 12 for irradiating the photocatalyst 11 with ultraviolet rays is provided on the lower surface of the partition wall 3 constituting the ceiling of the vegetable compartment 5 above the moisture permeable member 10. A lamp cover 13 for reflecting ultraviolet light is provided on the light source 12 mounting surface of the partition wall 3 by an adhesive means such as a double-sided tape. Thereby, the light source 1
UV light emitted from the lamp cover 13 directly and the lamp cover 13
Is reflected to irradiate the photocatalyst 11 on the moisture-permeable member 10.

With respect to the refrigerator configured as described above,
The operation will be described below.

Various foods are stored and stored in each storage room of the main body 1 according to the type. Vegetables such as vegetables and fruits are stored in the storage container 8 of the vegetable compartment 5.

[0015] Here, as the ripening of the vegetables and fruits themselves progresses, ethylene which promotes plant aging, acetaldehyde and ethanol which cause obstacles such as appearance deterioration, etc. are generated, and these gases are stored in the storage container 8. When the gas concentration exceeds the predetermined concentration, the aging of vegetables and fruits is accelerated.

However, even in such a case, the photocatalyst 11
On the other hand, the oxidative decomposition power generated by irradiating ultraviolet rays using the light source 12 removes aging promoting substances such as ethylene and acetaldehyde, thereby suppressing the aging promotion of vegetables and fruits in the storage container 8. The freshness of the fruits and vegetables stored in the vegetable room 5 can be maintained for a long period of time.

The moisture permeable member 10 carrying the photocatalyst 11
Is installed on the cover 9 above the storage container 8,
Ethylene, which is lighter than air and easily stays in the upper layer of the storage container 8,
The contact ratio with the photocatalyst 11 is high, and effective removal of ethylene becomes possible.

[0018]

However, since the above-mentioned conventional configuration is a configuration in which the photocatalyst 11 alone removes an aging-promoting substance such as ethylene, even if the photocatalyst 11 develops oxidative decomposition power, the photocatalyst 11 does not. Since decomposition occurs only when the aging promoting substance comes into contact with the surface, the decomposition rate of the aging promoting substance depends on the probability of contact between the photocatalyst 11 and the aging promoting substance, so that the removal efficiency is poor and the light source 12 is not irradiated. In a dark place, there is a disadvantage that the aging promoting substance cannot be removed at all.

In addition, in the above-described conventional configuration, when the light source 12 is continuously turned on to remove the aging-promoting substances such as ethylene, the power consumption of the refrigerator is increased and the temperature in the vegetable compartment 5 is also increased. There was a drawback to cause.

The present invention has been made to solve the conventional problems, and has a removing element in which a photocatalyst and an adsorbent are supported on one surface of a substrate and activated carbon having a palladium catalyst impregnated on the other surface of the substrate. By installing a removal device with a built-in light source in the vegetable room and increasing the removal rate of aging-promoting substances such as ethylene when the light source is not lit, the freshness retention period of fruits and vegetables is improved, and power consumption from the light source is reduced. It is another object of the present invention to provide a refrigerator capable of suppressing a rise in the temperature of the vegetable compartment.

Further, in the above-described conventional configuration, the light emitted from the light source 12 and having a wavelength of less than 400 nm
Does not reach the inner surface of the storage container of the moisture permeable member 10 carrying the water, and the aging-promoting substance such as ethylene produced from the fruits and vegetables passes through the through-hole opened in the moisture permeable member 10 to the outside of the storage container 8. For the first time, the photocatalyst 11 is decomposed by the activated photocatalyst 11 and the efficiency of removing the aging accelerating substance remaining in the storage container 8 is low.

Another object of the present invention is to use a white zeolite having a high light reflectance as an adsorbent of each removing element,
By irradiating all photocatalysts on the removal element with light containing a wavelength of less than 400 nm, a removal device with increased light use efficiency is installed in the vegetable compartment, and the removal rate of substances that promote aging of fruits and vegetables is improved. It is intended to provide a refrigerator.

Another object of the present invention is to provide a removing device that achieves both high ethylene removing performance and suppression of cost increase by using a removing element that optimizes the amount of high cost palladium catalyst adsorbed on activated carbon. An object of the present invention is to provide an on-board refrigerator.

[0024] Still another object of the present invention is to provide a method for supporting activated carbon to which a photocatalyst, an adsorbent and a palladium catalyst are applied on a porous substrate so that the performance of each catalyst can be maximized. An object of the present invention is to provide a refrigerator in which a removing device provided with a produced removing element is mounted in a vegetable room, and a removal speed of a substance that promotes aging of fruits and vegetables is further improved.

Still another object of the present invention is to provide a vegetable compartment with a removal device having a mechanism for regenerating the adsorption capacity of activated carbon to which a palladium catalyst is attached and for oxidizing and decomposing gas components desorbed during regeneration with a photocatalyst. An object of the present invention is to provide a refrigerator that can be mounted and maintain the ethylene removal performance of the removal element for a long period of time.

Still another object of the present invention is to mount a removing device in which two or more of the removing elements are arranged so as to surround a light source in a vegetable compartment to maximize a removing speed of a substance which promotes aging of fruits and vegetables. It is an object of the present invention to provide a refrigerator with a minimum height.

[0027]

According to a first aspect of the present invention, there is provided a removing element having a photocatalyst and an adsorbent supported on a base material, and activated carbon supported on the base material and having a palladium catalyst impregnated thereon. And a light source for exciting the photocatalyst, and a housing for accommodating the removal element and the light source and having a housing having a ventilation opening, wherein the light source comprises:
It irradiates light containing a wavelength of less than 00 nm, for example, against an aging promoting substance such as ethylene or ethanol generated from vegetables and fruits such as fruits and vegetables, ethylene reacts with water with activated carbon impregnated with a palladium catalyst. The chemical reaction is promoted to change to acetaldehyde, and the generated acetaldehyde is adsorbed by the adsorbent and activated carbon, and other gases such as ethanol are also removed by the adsorbent.

Further, when the light source is turned on to irradiate the photocatalyst carried on the removing element with light having a wavelength of less than 400 nm, the photocatalyst exhibiting the oxidative decomposition power causes the ethylene in the gaseous phase to develop. , Acetaldehyde and ethanol are decomposed, and the gas on the adsorbent is also decomposed by the photocatalyst, so that the aging-promoting substances such as ethylene and acetaldehyde in the vegetable compartment can be further reduced to a low concentration, and activated carbon to which a palladium catalyst is impregnated. The lighting time of the light source can be shortened by using together, and the power consumption of the refrigerator increases,
It has the effect that the temperature rise in the vegetable compartment can be minimized.

Further, since the adsorbent and the activated carbon are supported on the same base material, the gas adsorbed on the activated carbon is also decomposed by the photocatalyst, so that the partial pressure on the adsorbent surface is reduced. , The gas on the activated carbon is diffused to the adsorbent side, and the ability to adsorb the activated carbon can also be regenerated.

According to a second aspect of the present invention, in the first aspect, the removing element has a photocatalyst facing the light source, and the photocatalyst faces the light source. Light can be used efficiently, and the device itself can be miniaturized.

According to a third aspect of the present invention, in the first or second aspect, the adsorbent of the removing element is:
Light having a silica / alumina ratio of 100 or more and being a white adsorbent and having a wavelength of less than 400 nm emitted from the light source is attenuated by the white adsorbent on the light receiving surface of the removing element. The photocatalyst has an effect of being efficiently reflected and improving the light utilization efficiency of the supported photocatalyst, and capable of improving the oxidative decomposition power for the generated aging promoting substance.

According to a fourth aspect of the present invention, in the first or second aspect, the amount of the palladium catalyst impregnated is 0.5 wt% to 2.0 wt% based on the weight of the activated carbon.
%, And the amount of generated ethylene is about 20 ppm on average per day.
If 5% to 2.0% by weight of a palladium catalyst is impregnated, the amount of ethylene can be sufficiently removed, and in view of the fact that the palladium catalyst which is a noble metal material is very expensive, the ethylene removal performance and By optimizing the amount of attachment and minimizing the amount of attachment, there is also an effect of suppressing an increase in the cost of the removing element.

According to a fifth aspect of the present invention, in the first aspect of the present invention, the removing element is formed on the surface of the porous base material and carries the first adsorbent.
The layer and the outermost surface carry a photocatalyst, and on the outermost surface of the removal element, activated carbon impregnated with a photocatalyst and a palladium catalyst are located, whereby each catalyst is made of fruits and vegetables such as ethylene and ethanol. The most effective contact with the aging-promoting substance can be achieved, and this has the effect of increasing the efficiency of gas decomposition and removal.

According to a sixth aspect of the present invention, in the fifth aspect of the present invention, the removing element is provided near the activated carbon supporting surface.
A heating means having a calorific value of 0 kJ / h or more is provided. The heating means periodically applies heat energy to the activated carbon supporting surface of the removing element to desorb the aging promoting substance on the activated carbon. To regenerate the adsorption capacity.

The invention according to claim 7 is the invention according to claim 6, further comprising control means for controlling the operation of the heating means and the light source, wherein the control means is linked with the energization of the heating means. The light source is also turned on, and even when the aging promoting substance adsorbed on the activated carbon by the heating means is desorbed into the gas phase, the light source is turned on in conjunction with the energization of the heating means,
The photocatalyst supported on the same base material as the activated carbon exhibits an oxidative decomposition power, so that the desorbed aging accelerator has an effect of being decomposed and removed before being diffused,
Gas diffusion from the activated carbon to the adsorbent, which is caused by the decomposition of the gas on the adsorbent by the photocatalyst, is further promoted, and the regeneration efficiency of the adsorption capacity of the activated carbon is increased.

According to an eighth aspect of the present invention, in the first or second aspect, two or more removing elements are provided, and the photocatalyst-carrying surface of each removing element is opposed to the irradiation surface of the light source. Since the light source irradiation surface faces the photocatalyst carrying surface of the removal element, light containing a wavelength of less than 400 nm, which is emitted when the light source is turned on, can be efficiently used to express the oxidative decomposition power of the photocatalyst. This has the effect of maximizing the ability of the removal element to decompose the aging-promoting substance by the photocatalyst.

According to a ninth aspect of the present invention, there is provided the refrigerator according to the first or second aspect, wherein ethylene is produced from food stored in the refrigerator.
The concentration of an aging promoting substance such as ethanol can be kept low.
In addition, by using the activated carbon together with the palladium catalyst, the lighting time of the light source can be shortened, and the power consumption of the refrigerator and the rise of the temperature in the refrigerator can be minimized.

According to a tenth aspect of the present invention, there is provided a refrigerator capable of storing fruits and vegetables, wherein the removing device according to the first or second aspect is provided in a circulation air path of cooling air in the refrigerator. By using the circulation air path of the above, the concentration of the aging promoting substance in the whole storage can be efficiently reduced.

According to an eleventh aspect of the present invention, there is provided a refrigerator having a vegetable room for storing fruits and vegetables, wherein the removing device according to the first or second aspect is provided in the vegetable room, and is stored in the vegetable room. In contrast to aging-promoting substances such as ethylene and ethanol generated from fruits and vegetables such as vegetables and fruits, ethylene is converted to acetaldehyde by the chemical reaction with water promoted by activated carbon impregnated with a palladium catalyst. Adsorbent and activated carbon, and for other gases such as ethanol,
Since it is removed by the adsorbent, the concentration of the aging-promoting substance in the vegetable compartment can be reduced, and freshness of the fruits and vegetables can be maintained.

[0040]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of a refrigerator according to the present invention will be described below with reference to the drawings. The same components as those of the related art are denoted by the same reference numerals, and detailed description is omitted.

As the photocatalyst shown in the present invention, at least one selected from the group consisting of titanium dioxide, zinc oxide, tin oxide, zirconium oxide, tungsten oxide, iron oxide, strontium titanate and barium titanate is used. It was used as a component. Among them, titanium dioxide having a crystal structure of anatase type is preferable because it can exert sufficient oxidative decomposition power even with weak ultraviolet light.

Further, the light source shown in the present invention may be any one containing light having a wavelength of 400 nm or less, and further, one having a main peak of the irradiation wavelength of the light source in the ultraviolet region, for example, black light or black light. If it is a germicidal lamp,
This is particularly preferable because the oxidative decomposition power of the photocatalyst can be expressed more efficiently.

Further, the activated carbon shown in the present invention preferably has a specific surface area of 800 m ² / g or more, more preferably 1000 m ² / g or more. In addition, as the shape of the activated carbon, a granular material having a particle size of 100 microns or less,
It is preferable to minimize ventilation inhibition, and more preferably 10 microns or less.

Further, various salts of palladium are used as the palladium catalyst shown in the present invention. Among them, palladium chloride, which is a hydrochloride, is particularly preferred in view of safety and chemical stability. preferable.

(Embodiment 1) FIG. 1 is a longitudinal sectional view of a refrigerator according to Embodiment 1 of the present invention. FIG. 2 is a longitudinal sectional view showing a vegetable room in which the apparatus for removing an aging-promoting substance of the refrigerator of the embodiment is installed. FIG. 3 is a perspective view showing the removing device of the embodiment. FIG. 4 is a longitudinal sectional view showing the removing device of the embodiment.

1 to 4, reference numeral 1 denotes a refrigerator main body, which is constituted by a heat insulating box 2. Refrigerator body 1
Is provided with a refrigerator compartment 14, a vegetable compartment 5, and freezer compartments 4 and 15 from above. Each room has a door 16,7,
Food can be taken in and out by opening and closing 17, 18. 19 is a refrigerator compartment heat exchanger, 20 is a freezer compartment heat exchanger, and 21 is a refrigerator compartment fan. Although not shown in detail, a well-known refrigeration cycle is incorporated in the refrigerator body 1 and the refrigerator compartment The heat exchanger 19 cools the air in the refrigerator to an appropriate temperature, and the cool air discharged from the top of the refrigerator compartment 14 via the refrigerator compartment fan 21 passes through the slits on the entire bottom surface of the refrigerator compartment 14 and the vegetable compartment. Flow into 5. The cool air flowing into the vegetable compartment 5 passes outside the storage container 8 and returns to the refrigerator compartment heat exchanger 19 on the back of the refrigerator compartment 14, so that the fruits and vegetables in the storage container 8 are indirectly cooled, Drying is suppressed.

Reference numeral 22 denotes a removing device for removing substances such as ethylene and acetaldehyde which promote aging of fruits and vegetables. For example, when the removing device is attached to the top of the vegetable compartment 5, ethylene lighter than air is efficiently removed. The installation location is not limited to the top surface.
The removing device 22 includes a removing element 23 and a light source 24,
It is configured to be housed inside.

The material of the housing 25 is preferably a metal material because it is not affected by ultraviolet rays emitted from the light source 24, and stainless steel is more preferable from the viewpoint of rust prevention. The housing 25 has a ventilation slit (vent opening) 2.
6 is provided, and in the case of a specification in which a ventilation flow is generated in the vegetable compartment 5, the opening position of the slit 26 is
It is preferable to arrange so that the direction of the ventilation flow into 5 is in the same direction as the flow of the cool air in vegetable compartment 5.

As shown in FIG. 5, the removing element 23 is formed on a base material 27 having a ventilation cross section by using an activated carbon 29 having a photocatalyst 11 and an adsorbent 28 attached to one ventilation surface and a palladium catalyst attached to the other ventilation surface. Is an element that carries. Case 25
The positional relationship between the removing element 23 and the light source 24 in FIG.
As shown in FIG. 6 and FIG. 6, it is preferable that the ventilation surface supporting the photocatalyst 11 of the removing element 23 be disposed at a position facing the light source 24 in terms of efficiently exhibiting the oxidative decomposition power of the photocatalyst 11.

Next, the details of the removing element 23 will be described below.

The base material 27 is provided with a through-hole 2 through which air can flow, in order to increase the contact ratio between the base material 27 and an aging promoting substance such as ethylene.
7a, and it is particularly preferable to form a honeycomb-shaped cross section. As the material of the base material 27, it is preferable to use an inorganic fiber or an inorganic porous material from the viewpoint of increasing the surface area and preventing the photocatalyst 11 from decomposing and deteriorating the base material 27 itself.

The adsorbent 28 has silica (SiO ₂ ) and alumina (Al ₂ O ₃ ) as main components, and when the ratio of silica is 1 as alumina, the ratio of 100 or more has high hydrophobicity. It is preferable to use it in a space having a high humidity atmosphere due to moisture evaporating from fruits and vegetables like the vegetable room 5, and a hydrophobic zeolite such as the Absenz series manufactured by Union Showa Co., Ltd. can be used. In addition, since the adsorbent 28 has silica and alumina as main components, it has a white appearance and hardly absorbs ultraviolet rays.
Therefore, the light is easily reflected in multiple directions on the substrate 27 from the light source 24, and the light can be efficiently emitted to the photocatalyst 11 carried inside the honeycomb substrate 27.

As a method of attaching the palladium catalyst to the activated carbon 29, palladium chloride is used as the palladium catalyst, and first, 0.1 to 3N, preferably 0.5 to 3N.
A predetermined amount of palladium chloride is dissolved in a 1N aqueous hydrochloric acid solution. Next, a predetermined amount of activated carbon 29 is immersed in the solution, and the solution is agitated with a stirrer and left for 12 hours or more.
Thereby, the palladium chloride in the solution is adsorbed and carried on the activated carbon 29. After removing the activated carbon 29 from the solution, drain the water, rinse with pure water, put in a constant temperature furnace,
Activated carbon 29 carrying palladium chloride can be obtained by drying under a temperature condition of not less than ° C.

Here, 0.5 wt.
%, 2.0 wt%, and 10 wt% of the activated carbon 29 carrying palladium chloride were measured for ethylene removal performance, as shown in FIG. As can be seen from FIG. 7, the ethylene removal rate increases as the supported amount of palladium chloride increases. From the viewpoint of the ethylene removal rate, the amount of palladium chloride supported is preferably 10 wt% or more, but since palladium chloride is a noble metal-based material, the amount of palladium chloride used increases due to the removal element. 23 leads to an increase in cost. Therefore, the amount of ethylene actually generated from the fruits and vegetables stored in the vegetable compartment 5 is 20 ppm on average per day.
The amount of palladium chloride impregnated on activated carbon 29 is 0.5 wt%
To 2.0 wt%.

As a method of supporting the activated carbon 29 impregnated with the photocatalyst 11, the adsorbent 28 and the palladium catalyst on the base material 27, the particles of each of the photocatalyst 11, the adsorbent 28 and the activated carbon 29 are uniformly dispersed in a solvent. A dispersion of the photocatalyst 11, a dispersion of the adsorbent 28 and a dispersion of the activated carbon 29 were prepared, respectively.
First, the base material 27 is immersed in the dispersion liquid of the adsorbent 28, excess liquid is removed by a treatment such as nitrogen blowing, and then dried at 150 ° C. or higher. And dried again at 150 ° C. or higher. further,
An activated carbon 29 impregnated with a palladium catalyst is carried on a substrate 27 carrying an adsorbent 28 and a photocatalyst 11.
Since 9 needs to be carried on only one ventilation surface of the substrate 27, the substrate 27 is immersed as shown in FIG.

In FIG. 8, a container filled with a raw material liquid 30 in which activated carbon 29 particles are dispersed is provided with a mesh 31 for preventing the base material 27 from being completely immersed when the base material 27 is immersed. ing. This mesh 31 is attached near the liquid surface of the raw material liquid 30,
The dimension between the liquid and the liquid surface is set within １ ／ of the thickness of the base material 27. In the container thus configured, the substrate 2
While keeping the ventilation surface of 7 parallel to the liquid surface of the raw material liquid 30, the base material 27 was immersed, and nitrogen was blown from the non-immersed surface of the raised base material 27 to remove excess liquid. 150 ° C
By drying the base material 27 as described above, the activated carbon 29 with the palladium catalyst attached to only one ventilation surface of the base material 27 is obtained.
Can be carried.

By manufacturing the removing element 23 in the above steps, the photocatalyst 11 is provided on one of the ventilation surfaces of the removing element 23.
Is located on the outermost surface of the removing element 23 as shown in FIG.
On the other ventilation surface, activated carbon 2 carrying a palladium catalyst
9 is located on the outermost surface of the removing element.
1 can maximize light use efficiency, and the activated carbon 29 supporting a palladium catalyst can also maintain a high contact ratio with ethylene.

As for the solvent to be dispersed, the adsorbent 2
8. Activated carbon 2 impregnated with photocatalyst 11 and palladium catalyst
If a material containing a binder that can fix 9 to the base material 27 is used, it can be firmly supported. The use of a silica-based material as the binder
This is preferable because the photocatalyst 11 does not undergo oxidative decomposition. The amount of each material carried on the base material 27 can be adjusted by changing the weight concentration of each particle dispersed in the solvent.

In the present embodiment, the base material 27 of the photocatalyst 11
Is fixed using a binder, but the photocatalyst 1
When titanium dioxide is supported as 1, in a solution obtained by mixing a titanium alkoxide compound with an aqueous alcohol solution, for example, ethanol, and further adding nitric acid or diethylamine as an additive, the titanium alkoxide compound is hydrolyzed in the solution. After the formation of titanium hydroxide, the substrate 2 supporting the adsorbent 28 is placed in the solution in this state.
It is also possible to form titanium dioxide on the surface of the substrate 27 by immersing the substrate 7 and firing the immersed substrate 27 to cause a dehydration reaction.

The refrigerator configured as described above will be described below based on its operation.

The air cooled by the refrigerator compartment heat exchanger 19 by the operation of the refrigerator compartment fan 21 is supplied to the refrigerator compartment 14 and the vegetable compartment 5.
And is again guided to the refrigerator compartment heat exchanger 19.

Here, when fruits and vegetables such as vegetables and fruits are stored in the storage container 8 of the vegetable compartment 5, among these fruits and vegetables, particularly fruits and the like release ethylene and acetaldehyde during the maturation process. The released ethylene further promotes the growth of vegetables and fruits and accelerates aging, and acetaldehyde causes disorders such as deterioration in appearance of fruits with reduced physiological activity. When the substance flows in through the flow of cold air through the slit 26 of the removing device 22 installed on the top surface of the vegetable compartment 5, acetaldehyde and the like in the aging-promoting substance are removed by the adsorbent of the removing element 23. 28 and activated carbon 29, and when the palladium catalyst impregnated on activated carbon 29 comes into contact with ethylene, it is chemically converted to acetaldehyde. It is adsorbed to the activated carbon 29 Te.
In addition, since the activated carbon to which the palladium catalyst is impregnated is supported on the outermost surface of the removing element 23, the contact ratio with ethylene is high, and the chemical reaction from ethylene to acetaldehyde is efficiently promoted. 5 can suppress the increase in the concentration of the aging promoting substance and maintain the concentration at a low level.

Even when the removing device 22 is installed in the vegetable room 5 where the cool air does not flow, the removing element 23 removes the aging-promoting substances present in the vicinity thereof, so that the inside of the removing device 22 is removed. Therefore, the concentration of the aging-promoting substance is lower than the concentration of the aging-promoting substance in the whole vegetable compartment 5, and a difference in the concentration of the aging-promoting substance occurs inside and outside the removing device 22. Due to this concentration gradient, the aging promoting substance in the vegetable compartment 5 is diffused toward the inside of the removing device 22 and removed by the removing element 23.

Further, when the light source 24 is turned on and the photocatalyst 11 of the removing element 23 is irradiated with light having a wavelength of less than 400 nm, the photocatalyst 11 exhibits an oxidative decomposition power. Since the photocatalyst 11 is supported on the outermost surface of the removing element 23 and the adsorbent 28 is a white material,
The photocatalyst 11 carried on the removing element 23 efficiently and sufficiently expresses oxidative decomposition power.

Table 1 shows the measurement results of the ethylene removing performance in the vegetable room 5 in which the removing device 22 is installed.

[0066]

[Table 1]

The conditions for measuring the removal performance are as follows: vegetables and fruits shown in (Table 2) were stored in a vegetable compartment 5 having an inner volume of 70 liters.
This is a measurement of the ethylene concentration in the vegetable room 5 after a day.

[0068]

[Table 2]

Here, in the first embodiment shown in Table 1, the light source 24 is changed to 6
As a result of lighting for a time, the comparative example 1
2 is basically the same as that of FIG. 2, except that the removing element 23 does not support the activated carbon 29 to which the palladium catalyst is attached, uses only the absorbing agent 28 and the photocatalyst 11 and uses the light source 24 continuously. The result in the case of irradiation and the result in Comparative Example 2 are the results in the case of a blank in which the removing device 22 is not installed.

From the results shown in Table 1, it was confirmed that the ethylene concentration in the vegetable compartment 5 of the first embodiment was kept at 1/10 or less of the blank of the comparative example 2. Comparative Example 1
In the first embodiment, the light source irradiation time is ４ of the irradiation condition of Comparative Example 1, but the ethylene concentration is ５. It has been confirmed that the activated carbon 29 to which is added is effective in improving ethylene removal performance and reducing power consumption of the light source 24.

By irradiating the light to the removing element 23, the aging-promoting substances such as ethylene and acetaldehyde on the adsorbent 28 are oxidized and decomposed by the photocatalyst 11, and as a result, the adsorbing ability of the adsorbent 28 is regenerated. Furthermore, the aging-promoting substance on the activated carbon 29 supported on the same base material 27 also causes a gas partial pressure difference between the activated carbon 29 and the adsorbent 28 due to a decrease in the gas partial pressure on the surface of the adsorbent 28.
Therefore, the aging promoting substance on the surface of the activated carbon 29 diffuses toward the surface of the adsorbent 28 and is decomposed by the photocatalyst 11 on the adsorbent 28. Thereby, the adsorption capacity of the activated carbon 29 can also be regenerated, and the adsorption performance of the removal element 23 can be maintained for a long time.

Further, as shown in FIGS. 10 and 11, when a plurality of removal elements 23 are installed so as to surround the photocatalyst 11 with the ventilation surface facing the irradiation surface of the light source 24, the light source The use efficiency of light including a wavelength of less than 400 nm emitted from 24 is improved, and the removal performance of the removal device 22 for the aging-promoting substance can be maximized.

FIG. 12 shows the ethylene removal performance in the case of the configuration of FIG. The removal performance is 3 compared to the removal element 23 alone.
It was confirmed that it improved more than twice.

As described above, in the refrigerator of the present embodiment, in the base material 27 having a ventilation cross section, the activated carbon 29 having the photocatalyst 11 and the adsorbent 28 supported on one of the ventilation surfaces and the palladium catalyst impregnated on the other surface. , A removing device 22 including a light-emitting element 24 for exciting the photocatalyst 11 and a housing 25 for accommodating them, the housing 25 has a plurality of slits 26 for ventilation, Light source 24 is 4
Irradiation with light having a wavelength of less than 00 nm is performed.
In the inside, the removing element 23 is installed with the ventilation surface supporting the photocatalyst 11 facing the light source 24, and further, the removing device 22 is installed in the vegetable room 5. Even when fruits and vegetables such as vegetables and fruits are stored and aging promoting substances such as ethylene and ethanol are generated from the fruits and vegetables themselves, ethylene is promoted by the activated carbon 29 impregnated with a palladium catalyst to promote a chemical reaction with water, and acetaldehyde. Changes to

The produced acetaldehyde is adsorbed by the adsorbent 28 and the activated carbon 29, and other gases such as ethanol are also removed by the adsorbent 28, so that the concentration of the aging-promoting substance in the vegetable compartment 5 can be reduced. When the photocatalyst 11 which is always maintained at a low concentration and is turned on by the light source 24 to irradiate the photocatalyst 11 carried on the removing element 23 with light having a wavelength of less than 400 nm, the photocatalyst 11 exhibiting oxidative decomposition power Thus, ethylene in the gas phase in the vegetable compartment 5
Acetaldehyde, ethanol and the like are decomposed, and the gas on the adsorbent 28 is also decomposed by the photocatalyst 11, so that the aging-promoting substances such as ethylene and acetaldehyde in the vegetable compartment 5 can be further reduced to a low concentration, and the palladium catalyst is removed. The light source 24 is used in combination with the activated carbon 29 impregnated.
Can be shortened, and an increase in power consumption of the refrigerator and an increase in temperature in the vegetable room 5 can be minimized.

Further, the adsorbent 28 is further provided on the same base material 27.
And the activated carbon 29 are supported, the gas on the adsorbent 28 is also used for the gas adsorbed on the activated carbon 29.
By being decomposed by 1, the partial pressure on the surface of the adsorbent 28 decreases, the gas on the activated carbon 29 diffuses to the adsorbent 28 side, and the adsorption capacity of the activated carbon 29 can be regenerated.

The refrigerator of the present embodiment has a configuration in which a white adsorbent 28 having a silica / alumina ratio of 100 or more is supported as an adsorbent of the removing element 23.
The emitted light having a wavelength of less than 400 nm is efficiently reflected by the white adsorbent 28 on the light receiving surface of the removing element 23 without attenuating the intensity, and the light utilization efficiency of the supported photocatalyst 11 is improved. And the oxidative decomposition power for the aging-promoting substance generated in the vegetable compartment 5 can be improved.

Further, in the refrigerator of the present embodiment, the amount of the palladium catalyst impregnated on activated carbon 29 carried on removal element 23 is 0.5 wt% to 2. wt.
The amount of ethylene generated from the fruits and vegetables stored in the vegetable compartment 5 is about 20 ppm on average per day, and is 0.5 wt.
If the palladium catalyst is impregnated in an amount of 2.0% by weight to 2.0% by weight, the amount of ethylene can be sufficiently removed. Also,
The palladium catalyst, which is a noble metal-based material, is very expensive, but as described above, after optimizing the ethylene removal performance and the amount of attachment, minimizing the amount of attachment, the removal element 2
3 can suppress an increase in cost.

Further, in the refrigerator according to the present embodiment, the removing element 23 has a porous base material 27 having a ventilation surface.
Adsorbent 28 as a first layer on the surface of
The photocatalyst 11 is carried on the outermost surface as a layer, and the activated carbon 29 carrying the palladium catalyst is carried on one side of the ventilation surface. The photocatalyst 11 and the palladium catalyst are attached to the outermost surface of the removing element 23. Activated carbon 29 is located, whereby each catalyst can most efficiently come into contact with an aging-promoting substance for fruits and vegetables such as ethylene and ethanol, and the efficiency of gas decomposition and removal can be increased.

Further, the refrigerator of the present embodiment
The photocatalyst 11 supporting surface is arranged so as to surround the photocatalyst 11 supporting surface toward the irradiation surface of the light source 24 by using at least one removing element 23, and the irradiation surface of the light source 24 is surrounded by the photocatalyst 11 supporting surface of the removing element 23. Is emitted when the light source 24 is turned on.
Most of the light having a wavelength of less than 00 nm can be utilized without waste to express the oxidative decomposition power of the photocatalyst 11, and the ability of the removal element 23 to decompose the aging-promoting substance by the photocatalyst 11 can be maximized.

(Embodiment 2) FIG. 13 is a longitudinal sectional view showing a vegetable room in which a device for removing an aging-promoting substance of a refrigerator according to Embodiment 2 of the present invention is installed. FIG. 14 is a vertical cross-sectional view showing a device for removing an aging-promoting substance of the refrigerator of the embodiment.

In FIGS. 13 and 14, reference numeral 32 denotes a heating means, which is provided in the vicinity of a ventilation surface of the removing element 23 carrying activated carbon 29 to which a palladium catalyst is attached. FIG.
As shown in FIG. 5, in the housing 25 of the removing device 22, the light source 24 is provided near the ventilation surface carrying the photocatalyst 11 of the removing element 23, and the heating means 32 is provided near the ventilation surface carrying the activated carbon 29. Are located. The heating means 32 preferably has a calorific value of 30 kilojoules (kJ) / h or more, and more preferably has a thin shape such as a line heater from the viewpoint that the ventilation resistance of the removing element 23 can be minimized. .

A control means 33 is connected to the light source 24, the heating means 32 and the electric wiring. Control means 33
Has a function of periodically energizing the light source 24 and the heating means 32, and periodically turning on the light source 24 independently.
The control is such that the oxidative decomposition power of the photocatalyst 11 of the removing element 23 is developed, and when the heating means 32 is energized, the light source is simultaneously turned on in conjunction with the heating means 32.

The refrigerator configured as described above
The operation will be described below.

Here, the aging-promoting substances such as ethylene and acetaldehyde generated from vegetables and fruits such as fruits and vegetables stored in the storage container 8 of the vegetable compartment 5 ride on the flow of cool air to form the top surface of the vegetable compartment 5. Through the slit 26 of the removing device 22 installed in the inside. When the light source 24 is turned off, acetaldehyde and the like in the aging-promoting substance are adsorbed by the adsorbent 28 and the activated carbon 29 carried on the removing element 23, and the evaporation temperature is extremely low at -102 ° C and the amount of adsorption is small. Ethylene is chemically converted into acetaldehyde by the action of a palladium catalyst attached to the activated carbon 29 and is adsorbed on the activated carbon 29.

When the amount of gas adsorbed on the activated carbon 29 on the removing element 23 increases, the gas concentration on the surface of the activated carbon 29 increases, so that ethylene having a low evaporation temperature and high kinetic energy of molecules is adsorbed on the pores of the activated carbon 29. This makes it difficult to reduce the contact ratio with the palladium catalyst attached to the surface of the activated carbon 29, thereby reducing the removal ability. However, even in such a case, the heating means 32 is operated to apply heat energy to the activated carbon 29. , The kinetic energy of the adsorbed aging promoting substance such as acetaldehyde increases, and the aging promoting substance is desorbed from the adsorption site into the gas phase.

Further, the light source 24 is also turned on in conjunction with the operation of the heating means 32, and the photocatalyst 11 on the removing element 23 exhibits an oxidative decomposition power. Decomposed. For this reason, the aging promoting substance detached from the activated carbon 29 does not diffuse into the vegetable compartment 5 and does not affect the stored fruits and vegetables.

Further, when the light source 24 is turned on, the aging-promoting substance on the adsorbent 28 is also decomposed by the photocatalyst, the gas partial pressure on the surface decreases, and a difference occurs with the gas partial pressure on the activated carbon. For this reason, gas diffusion occurs from the activated carbon 29 toward the adsorbent 28, but the gas on the activated carbon 29 has a high kinetic energy due to the thermal energy added by the heating means 32, so that the gas diffusion rate also increases, Since the regeneration efficiency of the adsorption capacity of the activated carbon 29 is improved and the contact ratio between the palladium catalyst impregnated on the activated carbon 29 and the ethylene is also increased, the removing element 23 always maintains a high ethylene removing performance and maintains the freshness of the vegetable compartment 5. Performance can be maintained for a longer period.

As described above, the refrigerator of the present embodiment is provided with the heating means 32 having a heating value of 30 kilojoules (kJ) / h or more near the activated carbon 29 carrying surface of the removing element 23. By periodically applying thermal energy to the activated carbon 29 supporting surface of the removing element by the heating means 32, the aging promoting substance on the activated carbon 29 can be desorbed, and the adsorption capacity can be regenerated.

Further, the refrigerator of the present embodiment includes control means 33 for controlling the operation of heating means 32 and light source 24,
In conjunction with the energization of the heating means 32, the control means 33
4 is also configured to be turned on at the same time. Even when the aging promoting substance adsorbed on the activated carbon 29 by the heating means 32 is desorbed into the gas phase, it is linked to the energization of the heating means 32. The light source 24 is turned on, and the photocatalyst 11 supported on the same base material as the activated carbon 29 expresses oxidative decomposition power, so that the desorbed aging accelerator is decomposed before diffusing into the vegetable compartment 5. Adsorbent 2 by photocatalyst 11
The gas diffusion from the activated carbon 29 to the adsorbent 28 caused by the decomposition of the gas on the gas 8 is further promoted, the regeneration efficiency of the activated carbon adsorption capacity is increased, and the ethylene removal performance of the removal element 23 is maintained for a longer period. be able to.

[0091]

As described above, the first aspect of the present invention provides a removing element having a photocatalyst and an adsorbent supported on a base material, and an activated carbon supported on the base material and impregnated with a palladium catalyst. In an apparatus for removing an aging-promoting substance, comprising: a light source for exciting the photocatalyst; and a housing that houses the removing element and the light source and has an opening for ventilation, the light source includes:
It irradiates light containing a wavelength of less than nm, for example, against aging-promoting substances such as ethylene and ethanol generated from fruits and vegetables such as vegetables and fruits, ethylene reacts with water with activated carbon impregnated with a palladium catalyst. The chemical reaction is promoted to change to acetaldehyde, and the generated acetaldehyde is adsorbed by the adsorbent and activated carbon, and other gases such as ethanol are also removed by the adsorbent.

Further, when the light source is turned on to irradiate the photocatalyst carried on the removing element with light having a wavelength of less than 400 nm, the photocatalyst exhibiting oxidative decomposition power causes ethylene in the gaseous phase. , Acetaldehyde and ethanol are decomposed, and the gas on the adsorbent is also decomposed by the photocatalyst, so that the aging-promoting substances such as ethylene and acetaldehyde in the vegetable compartment can be further reduced to a low concentration, and activated carbon to which a palladium catalyst is impregnated. The lighting time of the light source can be shortened by using together, and the power consumption of the refrigerator increases,
It has the effect that the temperature rise in the vegetable compartment can be minimized.

Further, since the adsorbent and the activated carbon are carried on the same base material, the gas adsorbed on the activated carbon is also decomposed by the photocatalyst, so that the partial pressure on the adsorbent surface is reduced. , The gas on the activated carbon is diffused to the adsorbent side, and the ability to adsorb the activated carbon can also be regenerated.

According to a second aspect of the present invention, in the first aspect of the invention, the removing element has the photocatalyst facing the light source, and the photocatalyst faces the light source. Light can be used efficiently, and the device itself can be miniaturized.

According to a third aspect of the present invention, in the first or second aspect, the adsorbent of the removing element is:
Light having a silica / alumina ratio of 100 or more and being a white adsorbent and having a wavelength of less than 400 nm emitted from the light source is attenuated by the white adsorbent on the light receiving surface of the removing element. The photocatalyst has an effect of being efficiently reflected and improving the light utilization efficiency of the supported photocatalyst, and capable of improving the oxidative decomposition power for the generated aging promoting substance.

According to a fourth aspect of the present invention, in the first or second aspect, the amount of the palladium catalyst impregnated is from 0.5 wt% to 2.0 wt% based on the weight of the activated carbon.
%, And the amount of generated ethylene is about 20 ppm on average per day.
If 5% to 2.0% by weight of a palladium catalyst is impregnated, the amount of ethylene can be sufficiently removed, and considering that the palladium catalyst, which is a noble metal-based material, is very expensive, the ethylene removal performance and By optimizing the amount of attachment and minimizing the amount of attachment, there is also an effect of suppressing an increase in the cost of the removing element.

[0097] According to a fifth aspect of the present invention, in the first aspect of the present invention, the removing element is formed on the surface of the porous substrate and supports the first adsorbent.
The layer and the outermost surface carry a photocatalyst, and on the outermost surface of the removal element, activated carbon impregnated with a photocatalyst and a palladium catalyst are located, whereby each catalyst is made of fruits and vegetables such as ethylene and ethanol. The most effective contact with the aging-promoting substance can be achieved, and this has the effect of increasing the efficiency of gas decomposition and removal.

[0098] According to a sixth aspect of the present invention, in the fifth aspect of the present invention, the vicinity of the activated carbon supporting surface of the removing element is set at 3.
A heating means having a calorific value of 0 kJ / h or more is provided. The heating means periodically applies heat energy to the activated carbon supporting surface of the removing element to desorb the aging promoting substance on the activated carbon. To regenerate the adsorption capacity.

The invention according to claim 7 is the invention according to claim 6, further comprising control means for controlling the operation of the heating means and the light source, the control means interlocking with the energization of the heating means. The light source is also turned on, and even when the aging promoting substance adsorbed on the activated carbon by the heating means is desorbed into the gas phase, the light source is turned on in conjunction with the energization of the heating means,
The photocatalyst supported on the same base material as the activated carbon exhibits an oxidative decomposition power, so that the desorbed aging accelerator has an effect of being decomposed and removed before being diffused,
Gas diffusion from the activated carbon to the adsorbent, which is generated by the decomposition of the gas on the adsorbent by the photocatalyst, is further promoted, and the regeneration efficiency of the adsorption capacity of the activated carbon is increased.

According to an eighth aspect of the present invention, in the first or the second aspect of the present invention, two or more removing elements are provided, and the photocatalyst-carrying surface of each removing element faces the irradiation surface of the light source. Since the light source irradiation surface faces the photocatalyst carrying surface of the removal element, light containing a wavelength of less than 400 nm, which is emitted when the light source is turned on, can be efficiently used to express the oxidative decomposition power of the photocatalyst. This has the effect of maximizing the ability of the removal element to decompose the aging-promoting substance by the photocatalyst.

According to a ninth aspect of the present invention, the removing device according to the first or second aspect is provided in a refrigerator, and ethylene, which is generated from food stored in the refrigerator, is removed.
The concentration of an aging promoting substance such as ethanol can be kept low.
In addition, by using the activated carbon together with the palladium catalyst, the lighting time of the light source can be shortened, and the power consumption of the refrigerator and the rise of the temperature in the refrigerator can be minimized.

According to a tenth aspect of the present invention, there is provided a refrigerator capable of storing fruits and vegetables, wherein the removing device according to the first or second aspect is provided in a circulation air path of cooling air in the refrigerator. By using the circulation air path of the above, the concentration of the aging promoting substance in the whole storage can be efficiently reduced.

According to an eleventh aspect of the present invention, there is provided a refrigerator having a vegetable room for storing fruits and vegetables, wherein the removing device according to the first or second aspect is provided in the vegetable room, and is stored in the vegetable room. In contrast to aging-promoting substances such as ethylene and ethanol generated from fruits and vegetables such as vegetables and fruits, ethylene is converted to acetaldehyde by the chemical reaction with water promoted by activated carbon impregnated with a palladium catalyst. Adsorbent and activated carbon, and for other gases such as ethanol,
Since it is removed by the adsorbent, the concentration of the aging-promoting substance in the vegetable compartment can be reduced, and freshness of the fruits and vegetables can be maintained.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view of a refrigerator according to a first embodiment of the present invention.

FIG. 2 is a longitudinal sectional view showing a vegetable room in which the apparatus for removing an aging promoting substance of the refrigerator according to the embodiment is installed.

FIG. 3 is a perspective view showing an apparatus for removing an aging-promoting substance of the refrigerator according to the embodiment;

FIG. 4 is a longitudinal sectional view showing an apparatus for removing an aging-promoting substance of the refrigerator according to the embodiment;

FIG. 5 is a perspective view of a removing element of the refrigerator according to the embodiment;

FIG. 6 is a plan view showing an arrangement relationship between a light source and a removing element of the refrigerator according to the embodiment;

FIG. 7 is a characteristic diagram showing the relationship between the amount of palladium chloride carried on the activated carbon of the embodiment and the ethylene removal performance.

FIG. 8 is a process chart showing a method for manufacturing the removal element of the embodiment.

FIG. 9 is an enlarged sectional view of the surface structure of the photocatalyst and adsorbent supporting surface of the removing element of the refrigerator according to the embodiment;

FIG. 10 is a longitudinal sectional view showing a device for removing an aging-promoting substance of the refrigerator according to the embodiment;

FIG. 11 is a plan view showing an arrangement relationship between a light source and a removing element of the refrigerator of the embodiment.

FIG. 12 is a characteristic diagram showing ethylene removal performance when a plurality of removal elements are installed in the refrigerator of the embodiment.

FIG. 13 is a longitudinal sectional view showing a vegetable room provided with a device for removing an aging-promoting substance of a refrigerator according to a second embodiment of the refrigerator of the present invention;

FIG. 14 is a longitudinal sectional view showing a device for removing an aging-promoting substance of the refrigerator according to the embodiment;

FIG. 15 is a plan view showing an arrangement relationship of a light source, a removing element, and a heating unit of the refrigerator of the embodiment.

FIG. 16 is a longitudinal sectional view showing a vegetable room of a conventional refrigerator.

[Explanation of symbols]

 5 Vegetable room 11 Photocatalyst 22 Removal device 23 Removal element 24 Light source 25 Housing 26 Slit (opening for ventilation) 27 Base material 28 Adsorbent 29 Activated carbon 32 Heating means 33 Control means

Claims (11)

[Claims] 1. A removing element having a photocatalyst and an adsorbent supported on a base material, activated carbon supported on the base material and having a palladium catalyst attached thereto, a light source for exciting the photocatalyst, the removing element and the light source And a housing having a ventilation opening, wherein the light source emits light having a wavelength of less than 400 nm. 2. The removing device according to claim 1, wherein the removing element has a photocatalyst facing the light source. 3. The removing apparatus according to claim 1, wherein the adsorbent of the removing element is a white adsorbent having a silica / alumina ratio of 100 or more. 4. The removal apparatus according to claim 1, wherein the amount of the palladium catalyst impregnated is in the range of 0.5 wt% to 2.0 wt% based on the weight of the activated carbon. 5. The removing element according to claim 1, wherein the removing element includes a first layer formed on the surface of the porous substrate and supporting the adsorbent, and a second layer supporting the photocatalyst on the outermost surface. The removal device according to any one of the preceding claims. 6. In the vicinity of the activated carbon supporting surface of the removing element, 30
The removal device according to claim 5, further comprising a heating unit having a heating value of kJ / h or more. 7. The apparatus according to claim 6, further comprising control means for controlling the operation of the heating means and the light source, wherein the control means turns on the light source in conjunction with energization of the heating means. The removal device as described. 8. The removing apparatus according to claim 1, wherein two or more removing elements are provided, and the photocatalyst-carrying surface of each removing element is arranged to face the irradiation surface of the light source. 9. A refrigerator provided with the removal device according to claim 1 in a refrigerator. 10. A refrigerator capable of storing fruits and vegetables,
A refrigerator, wherein the removal device according to claim 1 or 2 is provided in a circulation air path of cooling air in the refrigerator. 11. A refrigerator having a vegetable room for storing fruits and vegetables, wherein the removing device according to claim 1 or 2 is provided in the vegetable room.