JPH042350A - Aldehyde removing agent - Google Patents

Abstract

PURPOSE:To obtain a quick and excellent removing effect for aldehyde compounds by using fatty amino acid with an amino group thereof yet to be ionized and not bonded to other functional groups by a hydrogen bonding or the like. CONSTITUTION:An aldehyde removing agent has at least one effective component among at least one kind of metal salt and/or fatty amino diamino monocarboxylate compounds of fatty amino acid compounds comprising monoamino monocarboxylate compounds, diaminomonocarboxylate compounds, diaminodicarboxylate compounds, oxydiamino acid compounds and sulfur- containing amino acid compounds. The metal salt of the fatty amino acid prevents occurrence of ionization of an amino group and a hydrogen bonding thereof to maximize the removing performance of aldehyde compounds. The fatty amino acid diaminomonocarboxylate compounds cause ionization of one amino group and one carboxylic group by an intermolecular reaction to generate bipolar ions but leaving remaining aminos unchanged. Thus, this agent excels in adsorbing performance for aldehyde and moreover, absorption capacity per weight is very large.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an agent for removing aldehydes. Specifically, the present invention relates to a removal agent effective for purifying odorous gases mainly containing aldehydes such as formaldehyde and acetaldehyde.

[Conventional technology]

Aldehydes such as formaldehyde and acetaldehyde are harmful gases with a unique pungent odor. In particular, acetaldehyde is listed as one of the eight foul-smelling substances, and there are 0. The odor can be felt even when it is present at a very low concentration of 5 ppm. Furthermore, at a concentration of about 5 ppm, it is highly irritating to the eyes and throat, and prolonged contact can cause inflammation, which is not desirable from a health standpoint.

The sources of these aldehydes include factories that manufacture aldehydes and their derivatives, factories that manufacture and mold resins such as polyacetal resins that use aldehydes, and manufacturing and molding factories that use adhesives (phenolic adhesives) that use aldehydes. Factories used, especially plywood manufacturing factories, and living environments include cigarette smoke, the human body, human waste, the inside of refrigerators, and automobile exhaust gas.

In the factories mentioned above, aldehydes are generated at relatively high concentrations, whereas in the living environment, aldehydes are generated at relatively low concentrations of several ppm or less.

As a method for removing aldehydes such as those mentioned in 2, in factories where the concentration is high, there is a method using a catalyst in which platinum group elements, copper group elements, lanthanide elements, and actinide elements are supported on a carrier such as alumina. It has been known for some time that this can be removed by adsorption using activated carbon or silica gel.

However, in the former method of removal using a catalyst,
The catalyst is expensive, and the temperature at which catalytic oxidation occurs is only 200°C.
The temperature is higher than that, and it is inconvenient to handle. The latter method of adsorption removal using activated carbon or silica gel in the living environment attempts to remove aldehydes by physically adsorbing them within the pore structure of the adsorbent. in this case,
Depending on the type of adsorbent, there are some that cannot adsorb aldehydes at all, and even those that can adsorb aldehydes have a limit to their ability, and when they reach a saturated adsorption state, they can adsorb aldehydes and, conversely, absorb aldehydes from the surrounding air. In some cases, it may be released into the air and not be removed. Another method is to remove it by reacting with aldehyde using chemicals. For example, phenylhydrazine, 2.
Salts such as 4-dinitrophenylhydrazine are widely used substances for collecting and quantifying aldehydes, especially in 2.
4-dinitrophenylhydrazine hydrochloride is used for measuring acetaldehyde in the malodor prevention method, and is very effective in chemically removing acetaldehyde from the air. However, in order to use these as aldehyde removers, they must be dissolved in strong acids such as hydrochloric acid or sulfuric acid, which limits their use as general removers. In addition, aromatic amines, which have traditionally been used as substances that react with aldehydes, are cancer-causing substances and there are concerns about their effects on the human body, and the odor of these substances is too high for use in living spaces. This is undesirable because it may cause disgust to the human body.

JP-A-60-129054 discloses a deodorizing/deodorizing agent containing amino acids and their salts as active ingredients. This is intended for application in the food field, and the targeted odors are basic odors such as ammonia and trimethylamine, and sulfide odors such as hydrogen sulfide and methyl mercaptan. It is mainly used as an addition to foods, diluted with organic solvents and water.

[Purpose of the invention]

The present invention was made in view of the above circumstances, and has a rapid and excellent removal effect on aldehydes, is odorless, and, like activated carbon, reaches a saturated adsorption state with a relatively small amount of physical adsorption. The purpose is to provide an aldehyde remover that does not have any adverse effects on the human body.

[Structure of the invention]

As a result of extensive studies, the present inventors have discovered that the above object can be achieved by controlling the ionization of amino groups in aliphatic amino acids.

The aldehyde removing agent of the present invention is a metal salt of at least one kind of aliphatic amino acids consisting of monoaminomonocarboxylic acids, diaminomonocarboxylic acids, diaminodicarboxylic acids, oxyamino acids and sulfur-containing amino acids and/or aliphatic amino acids. The active ingredient is at least one of the group amino' diaminomonocarboxylic acids.

[Action of the invention]

The aldehyde removal performance of the aliphatic amino acid is maximized when its amino group is not ionized and when it is not bonded to other functional groups through hydrogen bonds or the like.

When the amino group is ionized or bonded to other functional groups, the adsorption reaction and catalytic reaction to aldehydes are inhibited, and the aldehyde removal performance is reduced.

Ionization occurs as follows. When a proton (H+) is easily released from the carboxyl group of the aliphatic amino acid, this proton converts the amino group within the same molecule into an ammonium ion.

As a result, the aliphatic amino acid becomes a zwitterionic ion in which the carboxyl group in the molecule is negatively ionized and the amino group is positively ionized. Further, when the aliphatic amino acid is placed in an acidic atmosphere, a proton is added to the amino group, and the amino group becomes an ammonium ion and ionizes.

Furthermore, hydrogen bonding between amino groups occurs as follows. When protons are difficult to release from the carboxyl group of the aliphatic amino acid, the amino group within the same amino acid molecule or the amino group within another molecule forms a hydrogen bond with the carboxyl group via the proton.

Therefore, in the present invention, by replacing the proton (H+) in the carboxyl group of the aliphatic amino acid with a metal ion, the ionization of the amino group of the amino acid by the proton and the hydrogen bonding of the amino group are prevented, thereby preventing the formation of aldehydes. Maximize removability.

Furthermore, aliphatic amino acid diaminomonocarboxylic acids have two amine groups and one carboxyl group in the molecule. Due to the above-mentioned intramolecular reaction, one amino group and one carboxyl group of the amino acid are ionized to become a zwitterionic ion, or the remaining amino groups are not ionized. Therefore, it has the same performance as metal salts of aliphatic amino acids.

In an aliphatic amino acid whose amino group is not ionized, the non-ionized amino group and carboxyl group act simultaneously and in concert to adsorb and remove aldehydes or inactivate them through a catalytic reaction.

〔Effect of the invention〕

As described above, the aliphatic amino acid metal salt and/or diaminomonocarboxylic acid of the present invention has excellent adsorption performance for aldehydes. In addition, metal salts of aliphatic amino acids and/or diaminomonocarboxylic acids have simple structures and small molecular weights, so the adsorption amount per weight is very large.

Furthermore, the main aliphatic amino acids used in the present invention are essential amino acids, including many that are designated as food additives. Therefore, it is harmless to the human body and the environment, and can be supplied at low cost.

Therefore, the aliphatic amino acid metal salt and/or diaminomonocarboxylic acid of the present invention can be used in large quantities as an aldehyde removing agent used in lower aldehyde manufacturing plants or products using the same. It is possible. It is also very effective as a variety of aldehyde removers used in homes, hospitals, etc. that directly affect human health, and can improve their safety.

[Other inventions]

The metal salts of the present invention include sodium salts, potassium salts,
Magnesium and calcium salts are preferred.

The metal salts of aliphatic amino acids and/or diaminomonocarboxylic acids of the present invention can be used as a powder or made into solutions of any concentration to increase the efficiency of contact with odors and enhance its effectiveness. Alternatively, it is preferable to support it in a highly dispersed state on a porous carrier.

Porous carriers include sepiolite, palygorskite, activated carbon, zeolite, activated carbon fiber, activated alumina,
In addition to inorganic porous carriers such as sepiolite mixed paper, silica gel, activated clay, alumina, vermiculite, and diatomaceous earth, organic porous carriers such as pulp, fiber, cloth, and porous polymer materials can be used. Its shape is sheet-like,
It may be honeycomb-shaped, powder-shaped, granular, granular, or plate-shaped.

The porous carrier itself has a low ability to adsorb aldehydes, or its ability to remove aldehydes is improved by supporting the aliphatic amino acid metal salt and/or diaminomonocarboxylic acid of the present invention. The method of supporting the metal salt of the aliphatic amino acid and/or the diaminomonocarboxylic acid on the porous carrier in a highly dispersed state is not particularly limited. It can be pulverized and mixed with a fine powder of a porous carrier, molded and supported, or it can be dissolved in a soluble solvent such as water, impregnated into a porous carrier with the solution, and then supported by evaporating the solvent. good.

In addition, as a method for industrially producing this aldehyde removing agent, for example, a metal salt of an aliphatic amino acid and/or a diaminomonocarboxylic acid and a porous carrier are mixed using a Henschel mixer, kneader, kneader, disper mill, etc. Mix using a machine. After drying, it can be ground in a grinder such as a Henschel mixer or hammer mill to form a powder or granular remover.

Additionally, this remover can be molded into a shape suitable for the intended use. For example, the above-mentioned powder can be kneaded with water, extruded with an extruder and dried as is, or cut into cylindrical tablets at regular intervals, or shaped into spherical tablets with a marmerizer. It may also be extruded into a honeycomb shape.

Furthermore, in order to impart strength to the removing agent, an organic binder such as polyvinyl alcohol or CMC, or an inorganic binder such as silica gel or diatomaceous earth may be added.

The amount of the aliphatic amino acid metal salt and/or diaminomonocarboxylic acid of the present invention supported on the porous carrier is:
For example, it is preferable that the amount is in the range of 0.1 to 30% by weight based on the carrier.

If the supported amount is less than 0.1% by weight, the aldehyde removal effect will be small, and if it exceeds 30% by weight, the dispersibility in the porous carrier will be poor, and the aldehyde removal performance will not only decrease, but also the porous carrier It inhibits its own adsorption properties for various gases.

More preferably, it is supported in a range of 0.5 to 15% by weight.

In addition, the monoamino monocarboxylic acids of the aliphatic amino acids of the present invention include glycine (NH7CH2C○OH),
Alanine (CH3CH(NH,,)COOH), Valine C(CH3) 2CHCH(NH2)COOH),
Leucine ((CH,)2CI-(CH2CH(NH2)
COOH), isoleucine (CH, CH2CH(CH3
diaminomonocarboxylic acids such as lysine (NH2(CH2), CH(
NH2)COOH), hydroxylysine (NH2CH2
CH(CH)(CH2)2CH(NH2)COOH),
Arginine ((NH)(NH2)CNH(CI-L'
) 3CH(NH2)COOH), asparaquine (N8
2COCH2CH(NH2')COOH), glutamine (NH2C○(CH2')2 CH(NH2)COOH
), and diaminodicarboxylic acids include cismethionine (HOOCCH(NH2)CH2S (CH2)2
CH(NH2)COOH), lanthionine ((HOOC
CH(NH2')CH2)2S), etc., and the amino acids include serine (HOCH2CH(NH2')CO
OH), threonine (CH, CH(OH)CH(NH2
')COOH), and the sulfur-containing amino acids include cysteine (H3CH2CH(NE(2)Co).

H), cystine ((SCH2CH(NH2)COOH)
2), methionine (CH3S (CH2)2CH(
NH2')COOH), etc.

Hereinafter, the present invention will be explained in detail with reference to examples, but the present invention is not limited by these examples unless it goes beyond the gist of the invention.

(Example) Table 1 shows the aldehyde removing agents of this example (Nα1 to Nα10) and the removing agents of comparative examples (No., C-1 to No., C-9).

0.1 g of each of the aldehyde removing agents (Nα1 to Nα10) of this example was weighed and placed in a gas-impermeable bag with a capacity of 54′. A predetermined amount of an aqueous aldehyde solution of a predetermined concentration was heated and vaporized, introduced together with air, sealed, and left at room temperature. After 24 hours, the concentration of acetaldehyde remaining in the bag was measured using a gas comatograph, and the adsorption amount (W) per 1 g of sample was determined according to the following equation (1), and the adsorption performance was compared.

Table 2 shows the measurement conditions of the gas chromatograph, and Table 3 shows the measurement results. As comparative examples, various aliphatic amino acids, salts of various aliphatic amino acids, and sodium O-aminobenzoate, which is a metal salt of aromatic amino acids, were taken up (Table 1 NαC-1 to NαC-9). The results of the adsorption performance test are also listed in Table 3.

・ ・ ・(1) Where, W: Adsorption amount (■/g) MW: Molecular weight of acetaldehyde■: Container capacity CF> Ca blank concentration (ppm) Cb: Residual concentration (ppm) W: Sample weight (g) Note that the blank concentration is the residual concentration when the same treatment is performed without placing the sample in a bag.

As is clear from the results in Table 3, it is 20 to 30 times as much as methionine hydrochloride and 2 to 3 times as
It exhibited high aldehyde adsorption performance, which was twice as high as that of other comparative examples.

As described above, the aldehyde removing agent of this example had unprecedented characteristics.

Claims (2)

[Claims] (1) At least one metal salt of aliphatic amino acids consisting of monoaminomonocarboxylic acids, diaminomonocarboxylic acids, diaminodicarboxylic acids, oxyamino acids and sulfur-containing amino acids and/or aliphatic amino acid diaminomonocarboxylic acid An aldehyde removing agent containing at least one type of acid as an active ingredient. (2) An aldehyde in which at least one metal salt of an aliphatic amino acid according to claim 1 and/or at least one aliphatic amino acid diaminomonocarboxylic acid as an active ingredient is supported in a highly dispersed state on a porous carrier. remover.