JP3091528B2 - Composite adsorbent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to industrial exhaust gas, tobacco odor generated in the living environment, body odor, human urine odor, food odor of refrigerators, ammonia contained in automobile exhaust gas, etc.
The present invention relates to a deodorizing material effective for removing malodors such as hydrogen sulfide and acetaldehyde, or an adsorbent for treating these gases.

[0002]

2. Description of the Related Art An offensive odor generated in a living environment such as an automobile, a kitchen, a living room, and an office is a complex odor in which various types of odors are mixed. For example, the odor in automobiles is a complex odor in which a cigarette odor, a sweat odor, an exhaust gas odor, a dusty odor and the like are mixed, and it is said that there are thousands of components. In the Offensive Odor Control Law, 12 kinds of components in these odors, namely, ammonia, methyl mercaptan, hydrogen sulfide, methyl sulfide, methyl disulfide, trimethylamine, acetaldehyde, styrene,
Propionic acid, normal butyric acid, normal valeric acid and isovaleric acid are specified as particularly important malodorous components.

Hitherto, as a method of removing such a bad smell, a method of masking using an aromatic agent, a method of adsorbing and removing it with activated carbon or silica gel, and the like have been adopted.

[0004] However, each of these methods has its own drawbacks. The method of masking with a fragrance does not fundamentally remove malodorous components, and the odor of the fragrance itself may be bothersome.
In the method using physical adsorption such as activated carbon and silica gel, the type of the adsorbent limits the types of odor components that can be adsorbed. For example, activated carbon had no effect on basic odors such as ammonia and trimethylamine.

Therefore, a chemical method has been devised as a method for solving these disadvantages. This is a method of chemically removing a malodor by a neutralization reaction, and can simultaneously remove both an acidic odor such as acetaldehyde and hydrogen sulfide and a basic odor such as ammonia and trimethylamine. That is,
The acidic odor is removed by neutralizing with a basic adsorbent and the basic odor is removed with an acidic adsorbent.

However, due to the nature of the basic adsorbent and the acidic adsorbent, when they are simultaneously supported on the same carrier or simultaneously dispersed in the same liquid, they react with each other and become deactivated. This has been a drawback of the composite adsorbent utilizing a chemical reaction.

Japanese Patent Publication No. 57-2368 discloses a method for removing a sulfur compound in which (1) an iodine or (and) iodine compound and (2) a boron compound or (and) a phosphorus compound are supported on activated carbon. ing.
However, in this method, the heat resistance of the iodine-supporting activated carbon catalyst is improved by a boron compound and / or a phosphorus compound, and the elimination of iodine or the iodine compound during the regeneration treatment is reduced. Elimination of the species was almost impossible.

[0008]

Accordingly, an object of the present invention is to provide a composite adsorbent capable of simultaneously removing both acidic odors such as acetaldehyde and hydrogen sulfide and basic odors such as ammonia and trimethylamine.

[0009]

Means for Solving the Problems The inventors of the present invention have overcome the above-mentioned drawbacks and have developed a composite adsorbent exhibiting excellent removal performance against a composite odor containing various malodorous components. As a result of intensive studies, they have invented the following composite adsorbent.

[0010] The composite adsorbent of the first invention has a structure in which an acidic salt of an m- and / or p-aromatic amino acid, an acid, and iodine and / or iodide coexist as active ingredients.

As the acidic salt of the m- or p-aromatic amino acid, the acidic salt of the m- or p-aromatic amino acid itself can be used. Furthermore, m- or p-
Starting from an aromatic amino acid or an alkali salt of the amino acid and adding an acid thereto, m- or p-
Ammonium ionization of the amino group of the aromatic amino acid,
It can also be an acidic salt of an aromatic amino acid. Further, at this time, by adding an acid in excess, m- or p-
The coexistence of an acidic salt of an aromatic amino acid and an acid can be formed.

The acid of the first invention includes, in addition to inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid, organic acids such as citric acid, malonic acid, malic acid and oxalic acid. It is preferable to use a nonvolatile acid such as sulfuric acid or oxalic acid. Further, as iodide, ammonium iodide, sodium iodide, potassium iodide and the like can be used.

Further, an aromatic monoaminomonocarboxylic acid is suitable as the aromatic amino acid. As the aromatic monoaminomonocarboxylic acid, m- or p-aminobenzoic acid and p-aminosalicylic acid are preferred.

Next, an example of a specific method for producing the composite adsorbent of the first invention will be described. m-aromatic amino acids,
An acid is excessively added to at least one of a p-aromatic amino acid and a salt of the amino acid, and at least one of iodine and / or iodide is added, whereby an acid salt of the amino acid, an acid, iodine and / or iodine are added. Alternatively, a composite adsorbent coexisting with at least one of iodides is produced.

Here, since the acid suppresses the reaction between the acid salt of the amino acid and iodine and / or iodide, at least one of the acid salt of the amino acid, the acid, iodine and / or iodide easily coexists.

The composite adsorbent of the second invention (corresponding to claim 3) is characterized in that the composite adsorbent of claim 1 is supported on a porous carrier in a highly dispersed state.

Examples of the porous carrier of the second invention include inorganic porous carriers such as sepiolite, palygorskite, activated carbon, zeolite, activated carbon fiber, activated alumina, sepiolite mixed paper, silica gel, activated clay, vermiculite, and diatomaceous earth. And organic porous carriers such as pulp, fiber, cloth, and porous polymer. Preferably, sepiolite, palygorskite, activated carbon, activated alumina or zeolite is used. Further, the type of the carrier can be freely selected depending on the type of the malodor generated.

The active ingredient of the first invention is co-supported on these porous carriers in a highly dispersed state. The porous carrier uniformly holds the active ingredient in the pores in its structure, increases the contact area with the odorous gas, and improves the odorous gas adsorption performance of the active ingredient. In addition, the performance of removing the odor of the adsorbent is further improved by the adsorption ability of the porous carrier itself. For example, activated carbon emits malodorous gases based on hydrocarbons,
Sepiolite adsorbs bad odor gases based on lower fatty acids well.

The shape of the porous carrier may be any of sheet, honeycomb, powder, granule, granule, plate, and fiber.

Further, the use form of the composite adsorbent of the invention according to the present invention is not particularly limited. These can be used as powders, but in order to enhance the effect, it is also effective to use them as solutions of any concentration.

Next, an example of a specific method for producing the composite adsorbent of the second invention will be described. The method of supporting the composite adsorbent of the second invention on a porous carrier is not particularly limited, but is preferably an acid salt of m-aromatic amino acid and / or p-amino acid.
A mixture comprising an acidic salt of an aromatic amino acid, an acid, and at least one of iodine and / or iodide is pulverized, mixed with a fine powder of a porous carrier, molded, and supported. More preferably, dissolved in water or other soluble solvents,
The porous carrier is impregnated with the solution and supported. By using such a solution, each component in the composite adsorbent can be simultaneously and uniformly supported on the porous carrier in a highly dispersed state, and the deodorizing performance of the components can be maximized. .

The total amount of the composite adsorbent carried is 0.1 to 0.1% based on the carrier.
It is preferred to be in the range of 30% by weight. Loading amount is 0.1
If the amount is less than 30% by weight, the effect of removing odors such as ammonia, acetaldehyde, and hydrogen sulfide is small, and 30% by weight.
If it exceeds, dispersibility in the porous carrier becomes poor, and not only the performance of removing odors such as ammonia, acetaldehyde, and hydrogen sulfide, but also the performance of adsorbing various gases of the porous carrier itself is reduced. More preferably 0.
It is preferable that the carrier be supported in the range of 5 to 15% by weight.

The compounding ratio of each component of the composite adsorbent can be freely selected depending on the malodorous component to be generated.

[0024]

The operation of the first invention will be described. Acid salts of m-, p-aromatic amino acids, despite being acidic substances,
It is effective in removing malodorous gases based on lower aldehydes which are acidic odors. This property is presumed to be caused by the simultaneous and concerted action of the acidified amino group and carboxyl group in the amino acid to chemically adsorb and remove lower aldehydes or to chemically inactivate lower aldehydes. In addition, the acid salification does not cause the coupling between the amino group and the carboxyl group to form zwitterion, so that the activity as the adsorbing and removing material does not decrease.

The acid removes basic malodorous gases such as ammonia and trimethylamine by a well-known acid-base reaction. Furthermore, while maintaining the acid chloride of the coexisting amino acids, the iodine ion generated by the coexisting iodine or iodide oxidizing and removing the sulfide is oxidized or acidified to be easily oxidized. It works to produce iodine again. It is considered that such an action sustains the activity of adsorbing and removing coexisting amino acids and iodine or iodide.

Further, since the amino acid is acidified and the iodine or iodide is oxidized with iodine, the amino acid and iodine or iodide are prevented from reacting and inactivating.

Iodine or iodide oxidizes and removes sulfide-based odorous gases such as hydrogen sulfide and methyl mercaptan. The reaction mechanism is presumed as follows.

That is, iodide produces hydroiodic acid by reaction with a coexisting acid. The resulting hydroiodic acid is oxidized to iodine by oxygen in the atmosphere or another oxidizing agent. This iodine oxidizes and removes sulfides. At this time, iodine again becomes iodide, which constitutes a circulation system that returns to the beginning of the reaction and forms iodine again, and does not excessively accumulate products such as sulfur and sulfide formed by oxidation of sulfide. As long as this reaction lasts forever.

Even when iodine itself is used as the adsorbent, since sulfides are oxidized and removed to form iodides, the same circulation system as above is formed thereafter.

Aromatic monoaminomonocarboxylic acid is particularly effective as a material for adsorbing and removing lower aldehydes because of its simple structure. Also, because of the stable structure,
Activity lasts for a long time.

Next, the operation of the second invention will be described. In the composite adsorbent of the second invention, an acidic salt of an amino acid, an acid, and at least one of iodine and / or iodide are coexistently supported on a porous carrier in a highly dispersed state on a carrier having a large specific surface area. Each component exerts its full potential. Also, if the carrier has activity such as adsorption properties,
Since the properties of the carrier are added to the activity of the loaded components, the activity of the entire composite adsorbent is further enhanced.

Furthermore, the components are uniformly and uniformly dispersed and maintained, and the interaction between the components proceeds smoothly to maintain the activity of each component.

[0033]

The composite adsorbent of the present invention can be used for any of malodorous gases based on lower aldehydes, sulfide-based malodorous gases such as methyl mercaptan and hydrogen sulfide, and basic malodorous gases such as ammonia and trimethylamine. Also shows excellent adsorption removal performance.

[0034]

【Example】

(Example 1) 6 parts by weight of p-aminobenzoic acid, 9 parts by weight of sulfuric acid, and 6 parts by weight of potassium iodide were dissolved in 100 parts by weight of water, and an aqueous solution in which p-aminobenzoic acid, sulfuric acid, and potassium iodide coexisted was dissolved. Produced. In this example, when the coexisting substance was formed, an amino acid group of p-aminobenzoic acid was added by adding excess sulfuric acid to p-aminobenzoic acid without directly using an acid salt of p-aminobenzoic acid. A proton was donated to form an ammonium ion and to form an acidic salt of p-aminobenzoic acid. Next, this aqueous solution (impregnation liquid No. 1) was mixed with coconut shell activated carbon 150 gm having a particle size of 4 to 6 mesh.
g was impregnated and dried by heating at 100 ° C. for 10 hours to obtain a composite adsorbent of this example (Sample No. 1).

An impregnating liquid No. 2 using m-aminobenzoic acid instead of p-aminobenzoic acid, an impregnating liquid No. 3 using oxalic acid instead of sulfuric acid, and ammonium iodide instead of potassium iodide The composite adsorbent of this example was produced using the impregnating liquid No. 4 using No. 4 (Sample Nos. 2 to 4). With respect to the obtained composite adsorbent, an acetaldehyde, ammonia, and hydrogen sulfide removal performance test was performed as follows.

1 g of each composite adsorbent was weighed and placed in a 5 liter gas impermeable bag. This bag contains 425 ppm acetaldehyde, 900 ppm ammonia, and 1000 ppm.
Each of them was sealed by introducing 0 ppm hydrogen sulfide, and left at room temperature. After 24 hours, the concentrations of acetaldehyde, ammonia and hydrogen sulfide remaining in the bag were measured. The result was obtained as a removal rate (%). The measurement was performed by a gas chromatograph for acetaldehyde and by a Kitagawa gas detector tube for ammonia and hydrogen sulfide. Table 2 shows the measurement conditions of the gas chromatograph, and Table 1 shows the measurement results.

For comparison, those carrying ammonium iodide and phosphoric acid, and those carrying p-aminobenzoic acid, phosphoric acid and cupric chloride were similarly removed from acetaldehyde, ammonia and hydrogen sulfide. The test was performed. The results are shown in Sample Nos. C-1 and C-
2 (the impregnating liquid at this time is referred to as impregnating liquid No. C-1 or C-2). In addition, the removal rate was calculated | required by Formula 1.

[0038]

[Table 1]

[0039]

(Equation 1)

[0040]

[Table 2]

Here, the blank concentration is the residual concentration when the same treatment is carried out without putting the adsorbent in the bag, and the blank concentrations of acetaldehyde, ammonia and hydrogen sulfide are 401.1 ppm, 820 ppm and 7 ppm, respectively.
It was 200 ppm.

As is evident from the results in Table 1, the composite adsorbent of this example had a remarkably improved performance as compared with the comparative product.

The composite adsorbent of this embodiment is used for automobiles, kitchens,
It is a composite adsorbent that is extremely useful in practical use and has an excellent effect on complex odors containing various malodorous components generated in living environments such as living rooms and offices, and is excellent for treating these gases. It can also be used as an adsorbent, carrier and the like.

The aromatic monoaminomonocarboxylic acid of this embodiment is particularly effective as a material for removing and adsorbing lower aldehydes, and the effect is stably maintained for a long period of time. In addition, since it is less toxic, it is a highly effective composite adsorbent that is highly effective in practical use, exhibiting an excellent effect on complex odors containing various odor components generated in the living environment such as automobiles, kitchens, living rooms, offices, etc. Become.

The composite adsorbent of this example has an acidic salt of an amino acid, an acid, and an iodide coexistently supported on a porous carrier in a highly dispersed state, and therefore has excellent mechanical strength and is easy to handle. It is. Accordingly, the composite adsorbent is practically extremely useful and can remove complex odors containing various malodorous components generated in living environments such as automobiles, kitchens, living rooms, and offices.

(Example 2) The corrosion resistance of SUS316L stainless steel in the impregnating solution prepared in Example 1 was examined by the following experiment.

A 1-liter glass container equipped with a reflux condenser was used as a test tank. A ribbon heater was wound around the side of the container, and the liquid temperature was kept constant at 80 ° C. The size and shape of the sample were round rods with a diameter of 10 mm and a length of 50 mm. The surface was wet-polished, washed and degreased with SiC emery paper up to number 1200 in order, and then the impregnating liquid No. 1 was used so that each sample did not come into contact. -Test tank containing No. 4 (liquid volume 6
00 ml). The number of samples was three for each sample. The test time was 100 hours. After the test, corrosion products on the sample surface were removed, and the weight loss was measured. Assuming that the sample is totally corroded, the average corrosion rate of three samples is m
m / year. For comparison, the impregnating liquid N
o. The test was also performed in C-2. Table 3 shows the results.

[0048]

[Table 3]

The impregnating liquid of this embodiment has less corrosiveness to stainless steel than the impregnating liquid of the comparative example, and does not damage the manufacturing apparatus or the mounting apparatus of the composite adsorbent.

Since the impregnating liquid of this embodiment does not use corrosive components, it does not damage the manufacturing apparatus due to corrosion or the like, and does not require frequent cleaning of the manufacturing apparatus or constant replacement of parts. . Therefore, the production cost is rarely increased. Thus, an acid salt of an amino acid, an acid,
A composite adsorbent coexisting with at least one of iodine and / or iodide can be easily and inexpensively produced.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI B01D 53/81 (72) Inventor Etsuo Sugiyama 7800 Chihama, Oto-cho, Ogasa-gun, Shizuoka Prefecture Inside Cataler Industry Co., Ltd. (72) Inventor Susumu Tanaka 7800 Chihama, Daito-cho, Ogasa-gun, Shizuoka Prefecture Examiner, Cataler Industry Co., Ltd. Shigehiro Toyonaga (56) References JP-A-2-180634 (JP, A) JP-A-60-132645 (JP, A) JP-A-56-113342 (JP, A) JP-A-2-174932 (JP, A) JP-A-3-296434 (JP, A) JP-A-63-147542 (JP, A) JP-A-61-68136 (JP, A) JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) B01J 20/22 A61L 9/01 B01D 53/81

Claims (3)

(57) [Claims] 1. An acid salt of an m- and / or p-aromatic amino acid, an acid, iodine and / or iodide,
A composite adsorbent which is made to coexist as an active ingredient. 2. The composite adsorbent according to claim 1, wherein the aromatic amino acid is an aromatic monoaminomonocarboxylic acid. 3. A composite adsorbent, wherein the composite adsorbent according to claim 1 is supported in a highly dispersed state on a porous carrier.