JPH07136502A - Adsorbent for ammonia and aldehyde and air purifying filter unit - Google Patents

Abstract

PURPOSE:To provide an adsorbent of a simple structure having high adsorbing performance for both of bad odorous components of aldehydes and ammonia and to obtain an air purifying filter unit having excellent adsorption performance for aldehydes and ammonia with little pressure loss and low production cost. CONSTITUTION:(1) Aminobenzene sulfonic acid is added by 3-50% to an activated carbon material having 0.25-1.1cc/g pore volume of pores having 10-100Angstrom pore diameter. (2) Activated carbon fibers having 0.25-1.1cc/g pore volume of pores having 10-100Angstrom pore diameter to which aminobenzene sulfonic acid is added by 3-50wt.% are electrically flocculated to a porous base body to obtain the air purifying filter unit.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an adsorbent for ammonia and aldehydes and an air cleaning filter unit. Such an adsorbent and an air purifying filter unit are air purifiers and air purifiers whose main purpose is to adsorb and remove aldehydes, which are the main components of tobacco odor, and ammonia, which is the main component of animal odors derived from pets. It is useful in fields such as air conditioners with air conditioners.

[0002]

2. Description of the Related Art Various adsorbents for cleaning air are known, depending on the odorous components (aldehydes, ammonia, etc.) in the air.

As an adsorbent for aldehydes, an adsorbent in which activated carbon is impregnated with an amine and a derivative of an amine is generally used. For example, JP-A-56-53744 discloses aniline, JP-A-59-88078 discloses polyalkylimine, JP-A-60-48138, JP-A-60-54669 and JP-A-60. -20273
Japanese Patent Laid-Open No. 1-28836 discloses amino alcohols.
The gazettes respectively disclose aldehyde adsorbents obtained by impregnating activated carbon with p-toluidine.

Further, as a method of adsorbing ammonia, a method of adhering an acidic substance such as a fatty acid to activated carbon and chemically adsorbing ammonia by a neutralization method is adopted.

Further, JP-A-5-23558 discloses that
As a composite adsorbent that simultaneously removes acidic odors such as acetaldehyde and hydrogen sulfide and basic odors such as ammonia, an adsorbent in which an acidic salt of an aromatic amino acid and at least three components of iodine and / or iodide coexist as active ingredients. Is disclosed.

The main malodorous components targeted for the air purifier for the purpose of removing the malodor in the room are the tobacco odor containing acetaldehyde as a main component and the animal odor containing pets containing ammonia as a main component. Therefore, the adsorbent used in the air cleaner is required to have good adsorption performance for both aldehyde and ammonia.

However, amines as an adhering material used for removing aldehydes are easily deteriorated by oxidation in air or adsorption of moisture in air.
Particularly, in the case of aromatic amines, the degree of deterioration thereof is remarkable, and for example, in JP-A-60-48138,
It is described that the aldehyde adsorption capacity of activated carbon impregnated with aniline deteriorates with time in air.

As an air cleaning filter unit used in an air cleaner, an air conditioner equipped with an air cleaner, etc., for example, a powdery activated carbon (average particle diameter 0.03) is obtained by bonding an adhesive to a porous base material such as urethane foam. ~ 0.
Adsorbents to which (about 1 mm) is attached are commercially available. With this type of adsorbent, the particle size of activated carbon is small, so if you try to increase the basis weight, the amount of adhesive also increases, so the pores of activated carbon are blocked, and the adsorption capacity exceeds a certain value. It cannot be increased. On the other hand, when the amount of adhesive is reduced, the amount of activated carbon dropped off becomes so large that it cannot be put to practical use.

When granular activated carbon (average particle size of about 0.5 to 2 mm) is used instead of the above powdered activated carbon,
Since the particle size increases and the surface area decreases, the adsorption rate decreases and the particles easily fall off. Furthermore, when attempting to adhere in multiple layers to a porous substrate, a very large amount of adhesive is required, so that the pores of activated carbon are blocked.

Adsorbents using paper or felt of activated carbon fiber (hereinafter referred to as ACF) are also known.
However, ACF paper cannot be used as a normal deodorizing filter because it has a high pressure loss due to its too high density. The same applies to the felt of the ACF.

A thin adsorbent obtained by subjecting ACF paper to honeycomb processing and thinly slicing honeycomb corrugated cardboard, which has a small pressure loss and a large ACF basis weight, has a large number of processing steps, resulting in a high processing cost. There is a problem that it becomes extremely high.

Japanese Examined Patent Publication No. 57-31453 proposes an adsorbent in which NCF in constituent elements is 1% or more, a specific surface area is 300 m ² / g or more, and a fiber length of 0.5 to 1 mm is implanted with ACF. There is. However, this adsorbent has a problem that the adsorbing property of aldehydes is low when it is used, for example, in an air cleaning unit for removing indoor tobacco odor.

The above-mentioned JP-A-56-53744, JP-A-59-88078 and JP-A-60-202.
Japanese Patent No. 735 discloses an adsorbent in which amines are impregnated on granular activated carbon, and these are said to be effective for adsorbing aldehydes. However, when these granular amine-impregnated adsorbents are attached to a porous substrate such as urethane foam and used for adsorption of aldehydes,
Similar to the case of the above-mentioned granular activated carbon, there are problems such as a decrease in adsorption rate, dropping from the base material, and clogging of pores by an adhesive.

[0014]

SUMMARY OF THE INVENTION Therefore, the main object of the present invention is to provide an adsorbent having a simple constitution and exhibiting good adsorption performance for both malodorous components of aldehyde and ammonia.

Further, the main object of the present invention is to provide an air cleaning filter unit which is excellent in the adsorption performance of ammonia and aldehydes, has a small pressure loss, and has a low manufacturing cost.

[0016]

Means for Solving the Problems As a result of repeated studies in view of the current state of the art as described above, the present inventor has found that in the case of attaching aminobenzenesulfonic acid to an activated carbon material having specific pore characteristics, It has been found that an adsorbent exhibiting good adsorption performance for both malodorous components of aldehyde and ammonia can be obtained without using other components.

When aminobenzenesulfonic acid and aromatic amine are impregnated on an activated carbon material having specific pore characteristics, the adsorption performance is less likely to deteriorate due to air oxidation or absorption of moisture in the air. It was found that the wood was obtained.

Furthermore, when aminobenzene sulfonic acid or aminobenzene sulfonic acid and an aromatic amine are impregnated on ACF having specific pore characteristics and this is electroflocked on a porous substrate, ammonia and aldehydes are used. It was found that an air purifying filter unit having excellent adsorption performance and low pressure loss can be obtained.

That is, the present invention provides the following adsorbent and air cleaning filter unit: Ammonia and aldehydes characterized by comprising 3 to 50% by weight of aminobenzenesulfonic acid impregnated on an activated carbon material having a pore diameter of 10 to 100 angstrom and a volume of 0.25 to 1.1 cc / g. Adsorbent.

2. Aminobenzenesulfonic acid is p-
The adsorbent for ammonia and aldehydes according to the above item 1, which is aminobenzene sulfonic acid.

3. 3. The adsorbent for ammonia and aldehydes according to the above 1 or 2, wherein the activated carbon material is activated carbon fiber.

4. The volume of pores having a pore diameter of 10 to 100 angstroms is 0.25 to 1.1 cc / g, and activated carbon fibers impregnated with 3 to 50% by weight of aminobenzenesulfonic acid are electro-planted on a porous substrate. Air purification filter unit.

5. The porous substrate has a thickness of 0.5 to 50 m
5. The air cleaning filter unit according to item 4, which is a sheet-shaped material of m.

6. The average length of activated carbon fiber is 0.0
Item 5. The air cleaning filter unit according to Item 4 or 5, which has a size of 5 to 5 mm.

7. A total of 3 to 50% by weight of aminobenzenesulfonic acid and aromatic amine are impregnated on an activated carbon material having a pore volume of 10 to 100 angstrom and a volume of 0.25 to 1.1 cc / g. Adsorbent for ammonia and aldehydes.

8. Item 8. The adsorbent for ammonia and aldehydes according to Item 7, wherein the ratio (molar ratio) of aminobenzenesulfonic acid: aromatic amine is 2: 3 to 3: 2.

9. Item 8. The adsorbent for ammonia and aldehydes according to Item 7, wherein the aminobenzenesulfonic acid is p-aminobenzenesulfonic acid and the aromatic amine is p-toluidine.

10. Item 10. The adsorbent for ammonia and aldehydes according to any one of Items 7 to 9, wherein the activated carbon material is activated carbon fiber.

11. The volume of pores having a pore diameter of 10 to 100 angstrom is 0.25 to 1.1 cc / g, and the total amount of aminobenzene sulfonic acid and aromatic amine is 3 to 5
An air cleaning filter unit in which activated carbon fibers impregnated with 0% by weight are electro-implanted on a porous substrate.

12. Item 12. The air cleaning filter unit according to item 11, wherein the ratio (molar ratio) of aminobenzenesulfonic acid: aromatic amine is 2: 3 to 3: 2.

13. Aminobenzenesulfonic acid is p-
Aminobenzenesulfonic acid, aromatic amine is p-
Item 12. The air cleaning filter unit according to item 11, which is toluidine.

14. The porous substrate has a thickness of 0.5 to 50
Item 14. The air cleaning filter unit according to any one of items 11 to 13 which is a sheet-shaped material having a size of mm.

15. The average length of the activated carbon fibers is 0.
Item 15. The air cleaning filter unit according to any one of items 11 to 14 having a size of 05 to 5 mm.

Hereinafter, the adsorbents of items 1 to 3 (first invention), the air cleaning filter unit of items 4 to 6 (second invention), and the adsorbents of items 7 to 10 (third invention). The invention) and the air cleaning filter unit of the above items 11 to 15 (the fourth invention) will be described in detail.

I. First invention The activated carbon material used in the first invention has a pore diameter of 10
~ 100 angstrom pore volume 0.25
It is required to be 1.1 cc / g. Pore diameter 10-1
If the volume of pores of 00 angstrom is less than 0.25 cc / g, the effect of impregnating aminobenzene sulfonic acid becomes insufficient. When the pore diameter is less than 10 angstroms, even if aminobenzenesulfonic acid is attached, only a flat surface is formed, and the malodorous component cannot be adsorbed and removed well. On the other hand, the pore diameter is 1
When it exceeds 00 angstrom, the surface area of the activated carbon material decreases, which is not preferable.

Typical examples of the activated carbon material as described above include:
Activated carbon fibers are exemplified, but the activated carbon material used in the present invention is not particularly limited as long as the above-mentioned pore characteristic conditions are satisfied.

In the first invention, aminobenzenesulfonic acid is impregnated on the activated carbon material as described above. As the aminobenzenesulfonic acid, any of o-, m- and p-aminobenzenesulfonic acid can be used,
More preferred is p-aminobenzenesulfonic acid. The amount of aminobenzene sulfonic acid added is 3 to the weight of the activated carbon material.
It is about 50%, more preferably about 10-40%.
If the amount of impregnation is too small, the effect of adsorption and removal of malodorous components will not be sufficient, whereas if the amount of deposition is too large, it will block the pores of the activated carbon material and rather inhibit the effect of adsorption and removal of malodorous components. To do.

The aminobenzene sulfonic acid adsorbed on the activated carbon material mainly produces aldehydes by its amino group.
It is also presumed that ammonia is chemisorbed by the sulfone group.

The adsorbent according to the first invention is not particularly limited, but is usually manufactured as follows.

First, the activated carbon material is dried at a temperature of about 100 to 140 ° C. for about 30 to 60 minutes. Next, an aqueous solution of aminobenzenesulfonic acid prepared in advance is uniformly applied to the activated carbon material by a method such as spraying or dipping, and then dried. The concentration of the aminobenzenesulfonic acid aqueous solution, the contact time between the activated carbon material and the aqueous solution, and the like may be appropriately determined according to the pore characteristics of the activated carbon material, the desired amount of aminobenzenesulfonic acid supported, and the like.

II. Second Invention The ACF used in the second invention is not particularly limited, but it is preferable to use one having a fiber diameter of about 5 to 30 μm and an average fiber length of about 0.05 to 5 mm. When the average fiber length is less than 0.05 mm, the ratio of covering with the adhesive increases, the ratio of closing the pores increases, and the basis weight decreases. On the other hand, the average fiber length is 5
If it exceeds mm, it becomes difficult to implant hair on the porous substrate, and therefore the basis weight cannot be increased. In addition, the rate at which the long fibers block the void portion of the porous substrate increases, and the pressure loss increases. The average fiber length of the ACF is more preferably about 0.1 to 2 mm, the average fiber length is about 0.3 to 0.7 mm, and the fiber length distribution is within ± 0.2 mm. Particularly preferred.

The ACF used in the second invention also has a pore volume of 10 to 100 angstroms and a pore volume of 0.2.
It is required to be 5 to 1.1 cc / g. Pore size is 10
When the thickness is less than angstrom, even if aminobenzenesulfonic acid is attached, only a flat surface is formed, and the malodorous component cannot be adsorbed and removed favorably. On the other hand, if the pore size exceeds 100 angstroms, AC
It is not preferable because the surface area of F is reduced. When the pore volume is less than 0.25 cc / g, the amount of aminobenzenesulfonic acid impregnated becomes insufficient.

The origin of ACF is not particularly limited, and may be any of coal-based, petroleum-based, phenol resin-based, PAN-based, cellulose-based and the like.

Also in the second invention, aminobenzenesulfonic acid is attached to the above ACF. As the aminobenzenesulfonic acid, any of o-, m- and p-aminobenzenesulfonic acid can be used, but p-aminobenzenesulfonic acid is more preferable. The amount of the aminobenzene sulfonic acid added is about 3 to 50%, preferably about 10 to 40% of the ACF weight. If the amount of impregnation is too small, the effect of adsorbing and removing the malodorous component becomes insufficient. On the other hand, if the amount of impregnation is too large, the pores of the ACF are blocked and the effect of adsorbing and removing the malodorous component is obstructed.

The porous substrate not only functions as a support for the ACF but also as a filter for the fluid to be treated. As the porous substrate, a foamed resin (for example,
Polyurethane foam, polypropylene foam, polyethylene foam, modified polyphenylene oxide foam, acrylonitrile-butadiene-styrene resin foam, unsaturated polyester foam, etc.), mesh sheet (metal, resin etc.), perforated plate (metal, resin etc.) Can be mentioned. Among these porous substrates, the ones made of a foamed resin are more preferable, and the foamed polyurethane is more preferable, because the amount of ACF flocking per filtration area can be increased. The size, shape, etc. of the porous substrate are not particularly limited, but the thickness is 0.5 to
It is preferable that the sheet has a shape of about 50 mm.

The basis weight of ACF with respect to the porous substrate is 5
It is preferably about 0 to 500 g / m ² . When the basis weight is less than 50 g / m ² , the adsorption performance is not sufficiently exhibited, while when it is more than 500 g / m ² , the manufacturing cost becomes high and the pressure loss also increases.

The air cleaning filter unit made of the flocked adsorbent according to the present invention can be manufactured by an electric flocking method such as an electrostatic flocking method. In electrostatic flocking, the down method or the up method can be adopted, or both can be used together.

FIG. 1 schematically shows a cross-sectional view of an example of a manufacturing apparatus by the down method for manufacturing a flocked adsorbent by dropping a flocked material (ACF in this case).

In the apparatus shown in FIG. 1, the hopper 1 for containing the ACF 3 is vibrated to drop the ACF. On the other hand, a porous substrate 5 having an adhesive (for example, an aqueous urethane resin liquid) applied on its surface
Are arranged on electrodes 9 (for example, electrodes made of wire mesh) connected to the high voltage generator 7. The high voltage generator 7 is
Further, it is connected to the upper electrode 11 and the lower electrode 13. When manufacturing the flocked adsorbent, the ACF is dropped in a strong electric field during corona discharge to flock the ACF in an upright state with respect to the porous substrate 5. The potential difference between the electrodes 9 and 11 is usually 1000-300.
It is about 00 KV, and more preferably 3000 to 100
It is about 00 KV. If the potential difference is too low, AC
It becomes difficult for F to stand upright on the porous base material 5, and when it is too high, it becomes difficult to uniformly implant ACF on the surface of the porous base material 5.

III. Third Invention The third invention is the same as the first invention except that the aminobenzenesulfonic acid and the aromatic amine are attached to the activated carbon material.

As the aminobenzenesulfonic acid, any of o-, m- and p-aminobenzenesulfonic acid can be used, but p-aminobenzenesulfonic acid is more preferable.

As the aromatic amine, aniline, o-,
Examples thereof include m- and p-toluidine, o-, m- and p-aminobenzoic acid and the like, but p-toluidine is more preferable.

The total amount of the aminobenzenesulfonic acid and the aromatic amine to be impregnated is about 3 to 50%, more preferably about 10 to 40% of the ACF weight. If the amount of impregnation is too small, the effect of adsorbing and removing the malodorous component becomes insufficient. On the other hand, if the amount of impregnation is too large, the pores of the ACF are blocked and the effect of adsorbing and removing the malodorous component is obstructed.

The ratio (molar ratio) of aminobenzene sulfonic acid as an adhering material and aromatic amine is usually the former: the latter = about 2: 3 to 3: 2, more preferably 1: 1.
It is about 1 to 1.1: 1.

In the third aspect of the invention, the aminobenzenesulfonic acid adsorbed on the activated carbon material chemisorbs aldehydes mainly by its amino group, and also ammonia by its sulfone group, while the aromatic amine is It is presumed that it forms a salt with the sulfone group of aminobenzenesulfonic acid to prevent the adsorption ability from deteriorating due to moisture absorption of the sulfone group.

IV. Fourth Invention The fourth invention is the same as the second invention except that the aminobenzenesulfonic acid and the aromatic amine are attached to the ACF.

As the aminobenzenesulfonic acid, any of o-, m- and p-aminobenzenesulfonic acid can be used, but p-aminobenzenesulfonic acid is more preferable.

As the aromatic amine, aniline,
o-, m- and p-toluidine, o-, m- and p
-Aminobenzoic acid and the like can be mentioned, but p-toluidine is more preferable.

The total amount of the aminobenzene sulfonic acid and the aromatic amine impregnated in the fourth invention, the ratio (molar ratio) of the aminobenzene sulfonic acid and the aromatic amine as an adhering material and the like are the same as in the third invention, The material and form of the porous base material, the ACF basis weight of the porous base material, the method for manufacturing the air cleaning filter, etc. are the same as those of the second invention.

[0060]

According to the present invention, an adsorbent having an excellent adsorption performance for ammonia and aldehydes can be obtained with a simple structure. In addition, since this adsorbent is particularly excellent in adsorption performance for ammonia and aldehydes, it can be used in air purifiers, air conditioners with air purifiers, etc., whose main purpose is to remove tobacco odors, animal odors of pets, etc. It is especially useful as an adsorbent.

Further, in the air cleaning filter unit according to the present invention, unlike the conventional product using powdered activated carbon or granular activated carbon, the ratio of ACF buried in the adhesive is reduced, so that the ratio of effective pores available for adsorption is reduced. As it increases, a large amount of ACF can be densely planted. Therefore,
It is possible to obtain an adsorbent having a high adsorption capacity by utilizing the high adsorption rate of ACF. In addition, ACF hardly falls off from the porous substrate. Further, the pressure loss during the adsorption operation is significantly reduced as compared with the air cleaning filter unit made of ACF felt. Such an air cleaning filter unit is extremely useful, for example, in the following applications.

Further, when aminobenzene sulfonic acid and aromatic amino acid are used together as an adsorbent, the decrease in adsorption ability due to air oxidation or absorption of water is suppressed, so that as an adsorbent or an air cleaning unit. Durability is significantly extended.

-Deodorizing filter for air cleaning-Deodorizing filter for warm air heaters and air conditioners-Filter for removing ozone-Other various deodorizing filters-Dust removing filter

[0064]

EXAMPLES Examples and comparative examples will be shown below to further clarify the features of the present invention.

The preparation of the adsorbent samples used in the following Examples and Comparative Examples and the evaluation of the adsorption performance of the samples were carried out as follows.

-Preparation of sample (1) The activated carbon material to be impregnated was dried at 105 ° C for 1 hour, and the loss on drying was measured to determine the water retention amount.

(2) The activated carbon material dried in the above (1) is put in a vat, and a solution obtained by dissolving a necessary amount of the adhesive agent in water having a weight equal to the above water holding amount is sprinkled on the activated carbon material, and then a roller is used. The solution was smoothed so that the solution was evenly distributed.

(3) The activated carbon material, in which the chemical solution obtained in the above (2) was immersed, was hung by wire mesh and air-dried for 1 day.
It was dried at 105 ° C. for 1 hour.

(4) The weight of the activated carbon material after drying was measured, and the amount of the impregnated drug was examined.

-Evaluation of adsorption performance 1. Isothermal adsorption line The equilibrium adsorption amount of acetaldehyde and ammonia was evaluated by the following procedure using the closed circulation test apparatus shown in FIG.

(1) Chamber 1 having an internal volume of 22 liters
The concentration of the substance to be adsorbed in 5 is adjusted. (2) The adsorbed substance whose concentration has been adjusted is sucked using the circulation pump 17, passed through the activated carbon material sample (0.5 g ± 0.1 g) 23 packed in the column 21 having an inner diameter of 25 mm, and then the chamber. Circulate to 15. The circulation flow rate is maintained at 5 liters / minute by the flow meter 19. The temperature during the test is 22 to 26 ° C.

(3) When the concentration of the substance to be adsorbed in the chamber 15 is lower than 90% of the set concentration, the substance to be adsorbed is newly replenished in the chamber 15 to maintain the set concentration.

The concentration control in the system is performed by the gas sampling port 2
It is carried out by measuring the concentrations of aldehyde and ammonia in the gas sample extracted from No. 5.

(4) One test time is 60 minutes, and 6
The amount of adsorption of the substance to be adsorbed is calculated from the weight increase of the sample after 0 minutes.

(5) The same test is repeated, and the adsorption amount at which the difference from the previous adsorption amount is 0 is determined as the equilibrium adsorption amount of the sample.

2. Attenuation curve Using the closed circulation type test apparatus shown in FIG.
After adjusting the concentration of the substance to be adsorbed therein to 100 ppm, the concentration of the substance to be adsorbed after a certain period of time was measured to obtain an attenuation curve. The operation method and conditions of the other devices are the same as in the case where the isothermal adsorption curve was obtained above.

Example 1 Pitched activated carbon fiber (trade name "Adol A-10", manufactured by Adol Co., Ltd.) having a pore volume of 10 to 100 angstrom and a pore volume of 0.5 cc / g was added to p-aminobenzene. Sulfonic acid 6.5%, 20% and 30% respectively
(Activated carbon fiber standard; the same applies hereinafter) Three kinds of samples impregnated were prepared and used to obtain the decay curves of acetaldehyde and ammonia.

FIG. 3 shows the decay curve of acetaldehyde for each sample, and FIG. 4 shows the decay curve of ammonia for each sample (however, only when the amount of impregnation is 20% and 30%).

In FIGS. 3 and 4 and the graphs shown later, the vertical axis represents the ratio (C / C ₀ × 100%) of the value C after the lapse of a predetermined time with respect to the initial value C _o .

Example 2 Pitched activated carbon fiber (trademark "Adol A-10", manufactured by Adol Co., Ltd.) having a pore volume of 10 to 100 angstrom and a pore volume of 0.5 cc / g was added to p-aminobenzene. A sample was prepared by impregnating sulfonic acid with 20% and used to obtain an isothermal adsorption line (25 ° C.) of acetaldehyde and ammonia. FIG. 5 shows an isotherm adsorption line of acetaldehyde, and FIG. 6 shows an isotherm adsorption line of ammonia.

Comparative Example 1 Pitch-based activated carbon fibers (trademark "Adol A-10", manufactured by Adol Co., Ltd.) having a pore volume of 10 to 100 angstrom and a pore volume of 0.5 cc / g were treated with acetaldehyde and ammonia. An attenuation curve (25 ° C) was obtained.
FIG. 7 shows the decay curve of acetaldehyde, and FIG. 8 shows the decay curve of ammonia.

By comparing Example 1 (FIGS. 3 and 4), Example 2 (FIGS. 5 and 6) and Comparative Example 1 (FIGS. 7 and 8), p-aminobenzenesulfonic acid is impregnated on the activated carbon fiber. As a result, it is clear that the adsorbed amount of acetaldehyde and ammonia increases, and particularly when the impregnated amount is 20%, a remarkable effect is obtained.

Comparative Example 2 Pitched activated carbon fiber (trademark "Adol A-10", manufactured by Adol Co., Ltd.) having a pore volume of 10 to 100 angstrom and a pore volume of 0.5 cc / g was added to p-aminocarboxylic acid. When the equilibrium adsorption amount of acetaldehyde having a concentration of 100 ppm at 22 ° C.
It was / g.

It is apparent that the addition of the aromatic monoamino acid is insufficient to improve the effect of adsorbing acetaldehyde and ammonia as compared with the case where p-aminobenzenesulfonic acid is attached.

Example 3 Pitched activated carbon fiber (trademark “Adol A-10”, manufactured by Adol Co., Ltd.) having a pore volume of 10 to 100 angstrom and a pore volume of 0.5 cc / g was added to p-aminobenzene. A sample was prepared by impregnating 20% of sulfonic acid, and using this, the amount of acetaldehyde decay after 30 minutes was determined. The results are shown in Table 1 as the residual rate (C / C ₀ × 100%).

Example 4 A sample was prepared by impregnating 10% of p-aminobenzenesulfonic acid with activated carbon fiber having a pore volume of 10 to 100 angstrom and a pore volume of 0.8 cc / g, and using this sample. Then, the residual rate of acetaldehyde after 30 minutes was calculated. The results are shown in Table 1.

Comparative Example 3 A sample was prepared by impregnating 10% of p-aminobenzenesulfonic acid with activated carbon fiber having a pore volume of 10 to 100 Å and a pore volume of 1.2 cc / g, and using this sample. Then, the amount of attenuation of acetaldehyde after 30 minutes was calculated. The results are shown in Table 1.

[0088]

[Table 1]

Comparing the results of Examples 3, 4 and Comparative Example 3, when the activated carbon has a pore volume of 10 to 100 angstrom and the volume of the pore is 0.5 cc / g, the adsorbed amount of acetaldehyde is Is clearly the largest.

Example 5 Average pore diameter 18 Å (pore diameter distribution 1
0 to 50 angstrom), pore volume 0.5 cc /
g, pitch-based ACF having a specific surface area of 1000 m ² / g (trademark “Adol A-10”, manufactured by Adol Co., Ltd., length 0.3
˜0.7 mm, and basis weight of 150 g / m ² ) 100 parts were admixed with 30 parts of p-aminobenzenesulfonic acid.

Urethane foam (100 mm x 100 mm
(X5 mm), an aqueous urethane resin solution was thinly applied with a spray gun, and the above ACF was electro-flocked with a potential difference of 5000 KV using the apparatus shown in FIG.

The pressure loss at 25 ° C. of the obtained product was as shown by the line A in FIG. Note that FIG. 9 shows the pressure loss at 25 ° C. of the adsorbent made of an ACF felt having a basis weight of 150 g / m ² (felted pitch-based ACF similar to that used in Example 5) at line B.
Show as. The excellent performance of the flocked adsorbent according to the invention is evident.

Further, the obtained flocked product was cut into a diameter of 38 mm, suspended in a container having a temperature of 25 ° C. and a capacity of 22 liters, and adsorbing acetaldehyde while internally circulating a gas having an initial acetaldehyde concentration of 100 ppm.

The results are shown in FIG.

Example 6 A hair transplant product was obtained in the same manner as in Example 5 except that the amount of p-aminobenzenesulfonic acid impregnated with 100 parts of pitch-based ACF was 20 parts.

The aldehyde adsorption performance is shown in FIG.

The excellent aldehyde adsorption performance of the products according to the invention is evident.

Example 7 Ammonia was adsorbed in the same manner as in Example 5 except that a gas having an initial ammonia concentration of 100 ppm was used.

The results are shown in FIG.

Example 8 Ammonia was adsorbed in the same manner as in Example 6 except that a gas having an initial ammonia concentration of 100 ppm was used.

The results are shown in FIG.

The excellent ammonia adsorption performance of the products according to the invention is evident.

Comparative Example 4 Instead of ACF, powdered coconut husk activated carbon (specific surface area 100
An adsorbent was produced according to Example 5 except that 0 m ² / g; average particle size 0.3 mm) was used.

In order to set the basis weight to 150 g / m 2,
Compared to the case of Example 5, although the large amount of adhesive was required, the loss of activated carbon was remarkable.

Comparative Example 5 PAN-based ACF (having a nitrogen content of 5.8%) having a pore volume of 0.5 to 30 angstroms and a pore volume of 0.5 cc / g and a nominal specific surface area of 1000 m ² / g is used. An adsorption test for acetaldehyde was conducted in the same manner as in Example 5 except for the above.

The results are shown in Table 2. In Table 2, C / C
_“0” indicates the concentration C after a lapse of a predetermined time with respect to the initial concentration C ₀ of acetaldehyde.

[0107]

[Table 2]

Since the product of this comparative example does not have para-aminobenzenesulfonic acid impregnated therein, it is clear that the product of the present invention is extremely inferior in the aldehyde adsorption performance.

Example 9 Pore volume of 0.5 cc in 500 parts of an aqueous solution containing 1.6 parts of p-aminobenzenesulfonic acid and 1 part of p-toluidine.
/ G of nitrogen adsorption BET 10 parts of pitch-based ACF (trademark "Adol A-10", manufactured by Adol Co., Ltd.) having a BET specific surface area of 1000 m ² / g was immersed and kept at room temperature for 5 minutes, and then at normal pressure at 110 ° C. It was dried for 3 hours to obtain an adsorbent according to the present invention. The total amount of p-aminobenzenesulfonic acid and p-toluidine impregnated in this adsorbent was 23% of the ACF weight, and the molar ratio of p-aminobenzenesulfonic acid and p-toluidine was 1: 1.1. Met.

Next, 0.5 g of the above-mentioned adsorbent just after production
Was used to prepare a decay curve of acetaldehyde and ammonia, and the residual ammonia ratio was obtained after 60 minutes. The results are shown in Table 3.

[0111]

[Table 3]

Example 10 The adsorbent obtained in Example 9 was used in a room atmosphere (temperature 20 ± 2 ° C.,
Humidity of 50 ± 5%) was used, and 0.5 g of the adsorbent after 15 days, 30 days, 60 days and 90 days was used to create an acetaldehyde and ammonia decay curve, and the residual ammonia rate after 60 minutes was calculated. I asked. The results are shown in Table 4.

[0113]

[Table 4]

Example 11 Example 9 except that 500 parts of an aqueous solution containing 2 parts of p-aminobenzenesulfonic acid and 2 parts of p-toluidine are used.
After obtaining the adsorbent in the same manner as described in (1), the adsorption performance of the adsorbent immediately after production was measured in the same manner as in Example 9, and in the same manner as in Example 10, the indoor atmosphere (temperature: 20 ± 2 ° C., humidity: 5).
The adsorption performance after retention was measured at 0 ± 5%).

The total amount of p-aminobenzenesulfonic acid and p-toluidine impregnated in the adsorbent was ACF.
It was 37% by weight and the molar ratio of p-aminobenzenesulfonic acid to p-toluidine was 1: 1.5.

The results are shown in Table 5.

[0117]

[Table 5]

Comparative Example 6 An adsorbent was obtained in the same manner as in Example 9 except that 500 parts of an aqueous solution containing 2 parts of p-toluidine was used, and then the initial adsorption performance was measured in the same manner as in Example 9. Example 1
Same as 0, indoor atmosphere (temperature 20 ± 2 ℃, humidity 50
The adsorption performance after retention was measured at (± 5%). The results are shown in Table 6.

The amount of p-aminobenzenesulfonic acid impregnated in the adsorbent was 18% of the ACF weight.

[0120]

[Table 6]

From the results shown in Examples 9 to 11 and Comparative Example 6, the adsorbent according to the second invention exhibited an excellent effect of adsorbing low-concentration acetoaldehyde and ammonia without being affected by the humidity in the air. It is clear that it will work for a long time.

Example 12 Average pore diameter 18 angstrom (pore diameter distribution 1
0 to 50 angstrom), pore volume 0.5 cc /
g, pitch-based ACF having a specific surface area of 1000 m ² / g (trademark “Adol A-10”, manufactured by Adol Co., Ltd., length 0.3
~ 0.7 mm, basis weight 150 g / m ² ) For 100 parts,
In the same manner as in Example 9, p-aminobenzenesulfonic acid and p-toluidine were attached.

The total amount of p-aminobenzenesulfonic acid and p-toluidine impregnated in ACF was ACF.
It was 23% by weight and the molar ratio of p-aminobenzenesulfonic acid to p-toluidine was 1: 1.1.

Urethane foam material (100 mm x 100 mm
(X5 mm), an aqueous urethane resin solution was thinly applied with a spray gun, and the above ACF was electro-flocked with a potential difference of 5000 KV using the apparatus shown in FIG.

The pressure loss at 25 ° C. of the obtained product was almost the same as the result shown as the line A in FIG.

Example 13 An acetaldehyde and ammonia decay curve was obtained in the same manner as in Example by using 0.5 g of the product obtained in Example 12.

The results were almost the same as those shown in FIGS. 3 and 4, respectively.

[Brief description of drawings]

FIG. 1 is a sectional view schematically showing an example of a manufacturing apparatus and a manufacturing method of an air cleaning filter unit according to the present invention by a down method.

FIG. 2 is a flow sheet showing an outline of a closed-circulation type test apparatus used in Examples of the present invention.

FIG. 3 is a decay curve of acetaldehyde obtained in Example 1.

4 is an attenuation curve of ammonia obtained in Example 1. FIG.

5 is an isothermal adsorption line of acetaldehyde obtained in Example 2. FIG.

FIG. 6 is an isotherm adsorption line of ammonia obtained in Example 2.

7 is a decay curve of acetaldehyde obtained in Comparative Example 1. FIG.

8 is an ammonia decay curve obtained in Comparative Example 1. FIG.

FIG. 9 is a graph showing pressure loss (A) at 25 ° C. of the air cleaning filter unit obtained in Example 5 and pressure loss (B) at 25 ° C. of the air cleaning filter unit made of ACF felt.

FIG. 10 is a graph showing the acetaldehyde adsorption performance of the air cleaning filter units obtained in Examples 5 and 6.

FIG. 11 is a graph showing ammonia adsorption performance of the air purification filter units obtained in Examples 7 and 8.

[Explanation of symbols]

 1 ... Hopper 3 ... ACF 5 ... Porous substrate 7 ... High voltage generator 9 ... Electrode 11 ... Upper electrode 13 ... Lower electrode 15 ... Chamber 17 ... Circulation pump 19 ... Flowmeter 21 ... Column 23 ... Sample 25 ... Gas sampling mouth

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location B01D 53/81 B01J 20/20 E 7202-4G C07C 309/46 7419-4H (72) Inventor Masuda Ichiryu 1-2-2 Hirano-cho, Chuo-ku, Osaka-shi, Osaka Prefecture Osaka Gas Co., Ltd. (72) Inventor Takahiro Ikeda 4-1-2, Hirano-cho, Chuo-ku, Osaka City, Osaka Prefecture (72) Inventor Susumu Fujita 4-1-2, Hirano-cho, Chuo-ku, Osaka City, Osaka Prefecture Osaka Gas Co., Ltd.

Claims (15)

[Claims] 1. An aminocarbon sulfonic acid is impregnated with 3 to 50% by weight of an activated carbon material having a pore volume of 10 to 100 angstrom and a volume of 0.25 to 1.1 cc / g. Adsorbent for ammonia and aldehydes. 2. The adsorbent for ammonia and aldehydes according to claim 1, wherein the aminobenzenesulfonic acid is p-aminobenzenesulfonic acid. 3. The adsorbent for ammonia and aldehydes according to claim 1, wherein the activated carbon material is activated carbon fiber. 4. A activated carbon fiber having a volume of 0.25 to 1.1 cc / g of pores having a pore diameter of 10 to 100 angstrom and having 3 to 50% by weight of aminobenzenesulfonic acid impregnated therein is used as a porous substrate. An air purifying filter unit that is made by electrically flocking the material. 5. The air cleaning filter unit according to claim 4, wherein the porous substrate is a sheet material having a thickness of 0.5 to 50 mm. 6. The activated carbon fiber has an average length of 0.05 to 5
The air cleaning filter unit according to claim 4 or 5, which has a size of mm. 7. A total of 3 to 3 aminobenzenesulfonic acid and aromatic amine are added to an activated carbon material having a pore volume of 10 to 100 angstrom and a volume of 0.25 to 1.1 cc / g.
An adsorbent for ammonia and aldehydes, which is impregnated with 50% by weight. 8. The ratio (molar ratio) of aminobenzenesulfonic acid: aromatic amine is 2: 3 to 3: 2.
Adsorbent for ammonia and aldehydes described in 1. 9. The adsorbent for ammonia and aldehydes according to claim 7, wherein the aminobenzenesulfonic acid is p-aminobenzenesulfonic acid and the aromatic amine is p-toluidine. 10. The adsorbent for ammonia and aldehydes according to claim 7, wherein the activated carbon material is activated carbon fiber. 11. An activity in which the volume of pores having a pore diameter of 10 to 100 angstroms is 0.25 to 1.1 cc / g and a total of 3 to 50% by weight of aminobenzenesulfonic acid and aromatic amine are impregnated. An air cleaning filter unit made by electro-implanting carbon fibers on a porous substrate. 12. The ratio (molar ratio) of aminobenzenesulfonic acid: aromatic amine is from 2: 3 to 3: 2.
The air cleaning filter unit according to 1. 13. The air cleaning filter unit according to claim 11, wherein the aminobenzenesulfonic acid is p-aminobenzenesulfonic acid and the aromatic amine is p-toluidine. 14. The air cleaning filter unit according to claim 11, wherein the porous substrate is a sheet material having a thickness of 0.5 to 50 mm. 15. The average length of activated carbon fibers is 0.05 to.
The air purification filter unit according to any one of claims 11 to 14, which has a size of 5 mm.