JP2009082786A - Aldehyde adsorbent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adsorbent excellent in adsorbing and removing an aldehyde such as acetaldehyde contained in cigarette fume which is one of the greatest causes of an odor in air. <P>SOLUTION: The aldehyde adsorbent is constituted of porous silica having a mean pore diameter of greater than 1 nm and a compound comprising an amino group and/or an imino group, which aldehyde adsorbent contains an amino group and/or an imino group in an amount of 1.0 to 20 mmol per gram of the aldehyde adsorbent and has a X-ray diffraction pattern with at least one peak at a position where d-spacing is greater than 2 nm. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an aldehyde adsorbent, and in particular, is an adsorbent excellent in low-concentration malodor gas adsorption. More specifically, it is an aldehyde adsorbent excellent in the adsorption and removal of aldehydes such as acetaldehyde contained in tobacco smoke, which is one of the biggest causes of bad odor in the air.

  Conventionally, adsorption methods using porous adsorbents such as activated carbon, alumina, and zeolite are known as methods for deodorizing malodorous gases. Zeolite has relatively high adsorption performance for basic gases such as ammonia and trimethylamine, and acidic malodorous gases such as isovaleric acid and acetic acid, but sulfur-containing malodorous gases such as hydrogen sulfide and methyl mercaptan, For aldehyde gases such as acetaldehyde and formaldehyde, almost no adsorption performance is shown. In order to improve the adsorption performance for formaldehyde gas, a water-based paint for indoor pollution control (for example, see Patent Document 1) or a copper compound, which is a combination of a nitrogen-containing compound capable of adsorbing aldehydes and natural zeolite or synthetic zeolite, is solid at room temperature. A deodorizing agent for hydrogen sulfide and methyl mercaptan supported on natural zeolite is proposed (for example, see Patent Document 2), but the effect is not sufficient.

JP 2000-095980 A (P1 to P7) JP-A-5-237375 (P1 to P10)

  An object of the present invention is to obtain an unprecedented aldehyde adsorbent excellent in adsorption / removability of aldehydes by supporting a compound having an amino group and / or an imino group in the pores of a porous silica material. .

That is, the present invention
(1) It contains a silica porous material having an average pore diameter larger than 1 nm and a compound having an amino group and / or imino group of 1.0 to 20 mmol / g (aldehyde adsorbent), and the distance d is larger than 2 nm. Aldehyde adsorbent having an X-ray diffraction pattern having at least one peak (2) It is produced by mixing a porous silica and a compound having an amino group and / or an imino group in a non-aqueous solvent. Aldehyde adsorbent

  According to the present invention, it is possible to provide an aldehyde adsorbent in which the adsorption / removal performance of aldehydes such as acetaldehyde is remarkably improved as compared with conventional products.

  The aldehyde adsorbent in the present invention includes a silica porous material having an average pore size larger than 1 nm and a compound having an amino group and / or an imino group, and the amino group and imino group content is 1.0 to 20 mmol / It is an aldehyde adsorbent which is g (aldehyde adsorbent).

  The silica porous body in the present invention is a substance mainly composed of silicon oxide having a porous structure.

  The average pore diameter, specific surface area, and pore volume of the aldehyde adsorbent in the present invention can be calculated from known nitrogen adsorption isotherms. More specifically, the average pore diameter can be calculated by a known BJH method, BET method, t method, DFT method, etc., and the specific surface area can be calculated by a known BET method, t method, α method, or the like. The pore volume can be calculated by a known BJH method, BET method, t method or the like.

  When the average pore diameter of the pores of the aldehyde adsorbent in the present invention is less than 1 nm, aldehyde adsorption may not be sufficient, and those exceeding 20 nm are substantially difficult to produce. Therefore, from the above viewpoint, the average pore diameter of the pores of the aldehyde adsorbent in the present invention is 1 to 20 nm, more preferably 1 to 10 nm, still more preferably 1 to 7 nm, most preferably 1 to 1 nm. 4 nm.

If the specific surface area of the aldehyde adsorbent in the present invention is less than 100 m ² / g, aldehyde adsorption may not be sufficient, and those having a specific surface area greater than 2000 m ² / g are substantially difficult to produce. . Therefore, from the above viewpoint, the specific surface area of the aldehyde adsorbent in the present invention is preferably 100-2000 m ² / g, more preferably 300~2000m ² / g, most preferably 500~2000m ² / g.

It is not particularly limited pore volume of aldehyde adsorbent in the present invention, ^preferably, 0.1cm ^{3 /g~3.0cm} 3 / the controlled ones may be a g, more preferably , 0.2cm ³ /g~2.0cm good those controlled such that ³ / g. When the pore volume is smaller than the above range, aldehyde adsorption may not be sufficient, and when the pore volume is larger than the above range, it is substantially difficult to produce.

  The regularity of the pores in the present invention can be confirmed by X-ray diffraction or the like.

  The X-ray diffraction pattern can be measured with an X-ray diffractometer (RINT ULTIMAII manufactured by Rigaku Corporation).

  The aldehyde adsorbent in the present invention preferably has an X-ray diffraction pattern having at least one peak at a position where the d interval is larger than 2 nm, and a relative intensity of more than 50% of the maximum peak where the d interval is larger than 2 nm. More preferably, it does not have a peak.

  Further, the aldehyde adsorbent in the present invention preferably has an X-ray diffraction pattern in which the relative intensity is greater than 50% of the strongest peak and no peak exists in the range of d interval from 1 nm to 2 nm. It is more preferable to have an X-ray diffraction pattern in which the relative intensity is greater than 30% and the d interval is in the range of 1 nm to 2 nm and no peak is present, and the relative intensity is greater than 20% of the strongest peak and the d interval is 1 nm. It is most preferable to have an X-ray diffraction pattern having no peak in the range of 2 to 2 nm.

  The amino group and / or imino group content of the aldehyde adsorbent in the present invention is preferably 1.0 to 20 mmol / g, more preferably 1.0 to 15 mmol / g from the viewpoint of aldehyde adsorption. 1.0 to 12 mmol / g is most preferable.

The amino group and / or imino group content of the aldehyde adsorbent in the present invention can be measured by, for example, a thermogravimetric apparatus. That is, from thermogravimetry at 100 ° C. to 600 ° C., <W (100 ° C.) mg-W (600 ° C.) mg> × (number of amino groups per molecule used + number of imino groups) / M. W. Thus, the amino group and / or imino group content (mmol) can be calculated. Further, qualitative analysis can be performed by infrared spectroscopy (IR).
[W (100 ° C.) mg: weight of aldehyde adsorbent after standing at 100 ° C. for 0.5 hours /
W (600 ° C.) mg: Weight of aldehyde adsorbent after standing at 600 ° C. for 0.5 hour /
M.M. W. : Molecular weight of aldehyde adsorbent]

  Although it does not specifically limit as a compound which has an amino group in this invention, For example, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, N-2 (aminoethyl) 3-aminopropyl trimethoxysilane N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, ethylenediamine, triethylenetetramine, phenylamine, 2-amino-2-hydroxymethyl-1,3-propanediol, urea , (Nucleic acid such as adenine, thymine, guanine, cytosine), (amino acid such as alanine, arginine, glutamine) and the like, and 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2 (aminoe Le) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, ethylenediamine is preferable. You may use these individually or in mixture of 2 or more types.

  Although it does not specifically limit as a compound which has an imino group in this invention, For example, a triethylenetetramine, a proline, a hydroxyproline, a nucleic acid etc. are mentioned, A triethylenetetramine is more preferable from the point of aldehyde adsorption | suction. You may use these individually or in mixture of 2 or more types.

  The aldehyde in the present invention is not particularly limited as long as it is a compound having an aldehyde group, and examples thereof include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, and crotonaldehyde.

  The aldehyde adsorbed by the aldehyde adsorbent in the present invention includes formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, crotonaldehyde, etc., but formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde are more preferable from the viewpoint of adsorption amount, and formaldehyde, acetaldehyde Are more preferred, and acetaldehyde is most preferred.

  The aldehyde adsorption amount in the present invention can be calculated by the following aldehyde adsorption test.

(Aldehyde adsorption test)
100 mg of aldehyde adsorbent was put into a “smell bag” (bag capacity: 3 L, bag size: 250 × 250 mm, material: polyester film / manufactured by ASONE CORPORATION) containing air containing 50 ppm of aldehyde at 25 ° C. After standing for 30 minutes, the aldehyde concentration in the head space in the odor bag was measured with a gas detector tube (manufactured by Gastec Co., Ltd.). After the concentration measurement, the air in the odor bag was newly replaced with air containing 50 ppm aldehyde, allowed to stand at 25 ° C. for 30 minutes, and then the aldehyde adsorption concentration was measured with a detector tube. This operation was repeated, and a total of three adsorption amounts were calculated.

  The method for producing a porous silica material in the present invention is not particularly limited. For example, an inorganic material is mixed with an organic material and reacted to form an inorganic material skeleton around the organic material as a template. A method of removing the organic substance from the obtained complex after forming a complex of the organic substance and the inorganic substance.

The inorganic raw material is not particularly limited as long as it is a silicon-containing inorganic substance. Examples thereof include substances containing silicates such as layered silicates and non-layered silicates, and substances containing silicon other than silicates. Examples of layered silicates include kanemite (NaHSi ₂ O ₅ · 3H ₂ O), sodium disilicate crystal (Na ₂ Si ₂ O ₅ ), macatite (NaHSi ₄ O ₉ · 5H ₂ O), and Iraite (NaHSi ₈ O ₁₇ · XH ₂ O), magadiite (Na ₂ HSi ₁₄ O ₂₉ · XH ₂ O), Kenyaite (Na ₂ HSi ₂₀ O ₄₁ · XH ₂ O) and the like. Non-layered silicates include water glass (sodium silicate). ), Glass, amorphous sodium silicate, tetraethoxysilane (TEOS), tetramethoxysilane (TMOS), tetramethylammonium (TMA) silicate, silicon alkoxide such as tetraethylorthosilicate, and the like. Examples of the substance containing silicon other than silicate include silica, silica oxide, and silica-metal composite oxide. These may be used alone or in admixture of two or more.

  Examples of the organic raw material to be used as a template include cationic, anionic, amphoteric and nonionic surfactants. You may use these individually or in mixture of 2 or more types.

  Examples of the cationic surfactant include primary amine salts, secondary amine salts, tertiary amine salts, and quaternary ammonium salts. Among these, quaternary ammonium salts are preferable. Amine salts are poorly dispersible in the alkaline region, so that the synthesis conditions are used only in the acidic range. However, the quaternary ammonium salts can be used regardless of whether the synthesis conditions are acidic or alkaline. .

  Quaternary ammonium salts include octyltrimethylammonium chloride, octyltrimethylammonium bromide, octyltrimethylammonium hydroxide, decyltrimethylammonium chloride, decyltrimethylammonium bromide, decyltrimethylammonium hydroxide, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, Dodecyltrimethylammonium hydroxide, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium hydroxide, octadecyltrimethylammonium chloride, octadecyltrimethylammonium bromide, octadecyltrimethylammonium hydroxide Behenyltrimethylammonium chloride, behenyltrimethylammonium bromide, behenyltrimethylammonium hydroxide, tetradecyltrimethylammonium chloride, tetradecyltrimethylammonium bromide, tetradecyltrimethylammonium hydroxide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium hydroxide And alkyl (8 to 22 carbon atoms) trimethylammonium salt and the like. You may use these individually or in mixture of 2 or more types.

  Examples of the anionic surfactant include carboxylate, sulfate ester salt, sulfonate salt, and phosphate ester salt. Among them, soap, higher alcohol sulfate ester salt, higher alkyl ether sulfate ester salt, sulfate Examples include oils, sulfated fatty acid esters, sulfated olefins, alkylbenzene sulfonates, alkylnaphthalene sulfonates, paraffin sulfonates, and higher alcohol phosphate salts. You may use these individually or in mixture of 2 or more types.

  Examples of amphoteric surfactants include sodium laurylaminopropionate, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine. You may use these individually or in mixture of 2 or more types.

  Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene secondary alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolinic acid derivative, polyoxyethylene polyoxypropylene alkyl ether And ether type such as polypropylene glycol and polyethylene glycol, and nitrogen-containing type such as polyoxyethylene alkylamine. You may use these individually or in mixture of 2 or more types.

When silicon oxide such as silica (SiO ₂ ) is used as an inorganic material, a layered silicate such as kanemite is first formed, a template that is an organic material is inserted between the layers, and a silicate molecule is formed between layers where no template exists. Then, the mold can be removed to form pores. When water glass or the like is used, silicate monomers are gathered around a template which is an organic raw material, polymerized to form silica, and then the template is removed to form pores.

  When a surfactant is used as the organic raw material and pores are formed using the surfactant as a template, micelles can be used as the template. Further, by controlling the alkyl chain length of the surfactant, the diameter of the template can be changed and the diameter of the pores to be formed can be controlled. Furthermore, by adding a relatively hydrophobic molecule such as trimethylbenzene or tripropylbenzene together with the surfactant, the micelles expand and larger pores can be formed. By using these methods, pores having an optimal size can be formed.

  When mixing an inorganic raw material and an organic raw material, an appropriate solvent may be used. Although it does not specifically limit as a solvent, Water, alcohol, etc. are mentioned.

  The mixing method of the inorganic raw material and the organic raw material is not particularly limited, but after adding ion-exchanged water having a weight ratio of 2 times or more to the inorganic raw material and stirring at 40 to 80 ° C. for 1 hour or longer, the organic raw material is added. Are preferably mixed.

  The mixing ratio of the inorganic raw material and the organic raw material is not particularly limited, but the ratio of the inorganic raw material to the organic raw material (weight ratio) is preferably 0.1: 1 to 5: 1, more preferably 0.1: 1 to 1. 3: 1.

  The reaction between the inorganic raw material and the organic raw material is not particularly limited. However, the reaction is preferably performed at a pH of 11 or more for 1 hour or more, and after the pH is adjusted to 8.0 to 9.0, the reaction may be performed for 1 hour or more. preferable.

  Examples of the method for removing the organic substance from the complex of the organic substance and the inorganic substance include a method in which the complex is filtered, washed with water and dried, then baked at 400 to 700 ° C., and extracted with an organic solvent or the like. .

  The method for producing the aldehyde adsorbent of the present invention is not particularly limited. For example, it is preferable to prepare by mixing a compound having an amino group and / or an imino group with a porous silica material in a non-aqueous solvent. The mixing ratio in this case is not particularly limited, but the weight ratio of silica and the compound having an amino group and / or imino group is preferably 1: 0.1 to 1: 5.

  Although it does not specifically limit as a non-aqueous solvent, For example, toluene, isopropyl alcohol, ethanol, acetone, etc. are mentioned.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to a following example.

Production Example 1
N-decyltrimethylammonium chloride [C ₁₀ H ₂₁ N (CH ₃ ) ₃ Cl], which is a surfactant, from 50 g of water glass No. 1 (SiO ₂ / Na ₂ O = 2.00) manufactured by Nippon Chemical Industry Co., Ltd. Was dispersed in 1000 ml of a 0.1 M aqueous solution and heated at 70 ° C. with stirring for 3 hours. Thereafter, 2N hydrochloric acid was added while heating and stirring at 70 ° C., the pH of the dispersion was lowered to 8.5, and the mixture was further heated and stirred at 70 ° C. for 3 hours. The solid product was once filtered, dispersed again in 1000 ml of ion exchange water, and stirred. This filtration / dispersion stirring was repeated 5 times, followed by drying at 40 ° C. for 24 hours. The dried solid product was fired in air at 550 ° C. for 6 hours to obtain porous silica A. By adding 1 g of silica porous material A and 0.25 g of 3-aminopropyltriethoxysilane in 100 ml of isopropyl alcohol, mixing at room temperature for 24 hours, filtering, and drying the filtrate at 40 ° C. for 24 hours. 1.11 g of the inventive aldehyde adsorbent A was obtained.

Production Example 2
50 g of No. 1 sodium silicate (SiO ₂ / Na ₂ O = 2.00) manufactured by Nippon Chemical Industry Co., Ltd. was used as a surfactant for behenyltrimethylammonium chloride [C ₂₂ H ₄₅ N (CH ₃ ) ₃ Cl]. The mixture was dispersed in 1000 ml of a 0.1 M aqueous solution and heated at 70 ° C. with stirring for 3 hours. Thereafter, 2N hydrochloric acid was added while heating and stirring at 70 ° C., the pH of the dispersion was lowered to 8.5, and the mixture was further heated and stirred at 70 ° C. for 3 hours. The solid product was once filtered, dispersed again in 1000 ml of ion exchange water, and stirred. This filtration / dispersion stirring was repeated 5 times, followed by drying at 40 ° C. for 24 hours. The dried solid product was fired in air at 550 ° C. for 6 hours to obtain a porous silica material B. 1 g of silica porous material B and 0.25 g of 3-aminopropyltriethoxysilane were added to 100 ml of isopropyl alcohol and mixed for 24 hours at room temperature, followed by filtration. The obtained solid was dried at 40 ° C. for 24 hours to obtain 1.14 g of the aldehyde adsorbent B of the present invention.

Production Example 3
In 100 ml of isopropyl alcohol, 1 g of porous silica B obtained in the above production example and 2.00 g of triethylenetetramine were added and mixed at room temperature for 24 hours, followed by filtration. The obtained solid was dried at 40 ° C. for 24 hours to obtain 1.67 g of the aldehyde adsorbent C of the present invention.

  When the average pore diameter of the obtained aldehyde adsorbents A, B and C was calculated from a known nitrogen adsorption isotherm (BJH method), the average pore diameter of the aldehyde adsorbent A was 1.65 nm, and the average fine diameter of the aldehyde adsorbent B was The pore diameter B was 3.42 nm, and the average pore diameter of the aldehyde adsorbent C was 2.35 nm.

When the specific surface area (BET method) and pore volume (BJH method) of the aldehyde adsorbents A and B were calculated by a known nitrogen adsorption method, the specific surface area of the aldehyde adsorbent A was 659.6 m ² / g, and the pore volume was It was 0.288 cm ³ / g. The specific surface area of the aldehyde adsorbent B was 783.2 m ² / g, and the pore volume was 0.680 cm ³ / g. Moreover, the specific surface area of the aldehyde adsorbent C was 683.1 m ² / g, and the pore volume was 0.350 cm ³ / g.

  The X-ray diffraction patterns of the obtained aldehyde adsorbents A, B and C were measured. The results are shown in FIGS. 1, 2 and 3, respectively.

  As shown in FIGS. 1, 2, and 3, the aldehyde adsorbents A, B, and C have an X-ray diffraction pattern having at least one peak at a position where the d interval is larger than 2 nm, and the d interval is larger than 2 nm. It did not have a peak of relative intensity greater than 50% of the maximum peak at.

  The amino group and imino group contents of the aldehyde adsorbents A, B, and C were calculated from the thermogravimetric measurement at 100 ° C. to 600 ° C. using the above formula. The numerical values to be substituted into the formula are M.P. for aldehyde adsorbents A and B. W. = 58.10, the number of amino groups = 1, for the aldehyde adsorbent C, M.I. W. = 146.2, amino group = 2, imino group number = 2. As a result of calculation using the above formula, the amino group content of the aldehyde adsorbent A is 1.32 mmol / g, the amino group content of the aldehyde adsorbent B is 1.67 mmol / g, and the imino group of the aldehyde adsorbent C. The content was 10.9 mmol / g.

Comparative Example 1
A comparative adsorbent X1.11 g was obtained in the same manner as in Production Example 1 except that water was used instead of isopropyl alcohol.

Comparative Example 2
A comparative adsorbent Y1.13 g was obtained in the same manner as in Production Example 2, except that water was used instead of isopropyl alcohol.

  The X-ray diffraction patterns of the adsorbents X and Y were measured. The results are shown in FIGS. 4 and 5, respectively.

  As shown in FIGS. 4 and 5, the adsorbents X and Y had an X-ray diffraction pattern having no peak at a position where the d interval was larger than 2 nm.

  The adsorbents X and Y were measured for pore distribution by a known nitrogen adsorption method (BJH method), and the average pore diameter was calculated. As a result, the average pore diameter of the adsorbent X was 1.62 nm, and the average pore diameter of the adsorbent Y was It was 3.51 nm.

  Specific surface areas (BET method) and pore volumes (BJH method) of the adsorbents X and Y were calculated by a known nitrogen adsorption method.

The specific surface area of the adsorbent X was 670.2 m ² / g, and the pore volume was 0.291 cm ³ / g. The specific surface area of the adsorbent Y was 800.1 m ² / g, and the pore volume was 0.682 cm ³ / g.

  The amino group and imino group contents of the aldehyde adsorbents X and Y were calculated from the thermogravimetry at 100 ° C. to 600 ° C. using the above-described calculation formula. In addition, the numerical value substituted into the formula is M. for aldehyde adsorbents X and Y. W. = 58.10, number of amino groups = 1 was used. As a result of calculation using the above calculation formula, the adsorbent X has an amino group and / or imino group content of 1.29 mmol / g, and the adsorbent Y has an amino group and / or imino group content of 1.52 mmol / g. Met.

Aldehyde adsorption test Test example 1 Formaldehyde adsorption test Production example 1, Production example 2, Production example 3, Comparative example 1, Comparative example 1, Aldehyde adsorbent A, aldehyde adsorbent B, aldehyde adsorbent C, adsorbent X Adsorbent Y, activated carbon (average pore diameter: 0.8 nm, specific surface area: 800 m ² / g, pore volume: 0.4 cm ² / g, amino group and / or imino group content: 0 mmol / g) The following aldehyde adsorption test was conducted.
(Aldehyde adsorption test)
100 mg of aldehyde adsorbent was put into a “smell bag” (bag capacity: 3 L, bag size: 250 × 250 mm, material: polyester film / manufactured by ASONE CORPORATION) containing 2.5 L of air containing 50 ppm of aldehyde (formaldehyde), After standing at 25 ° C. for 30 minutes, the aldehyde (formaldehyde) concentration in the head space in the odor bag was measured with a gas detector tube (manufactured by Gastec Co., Ltd.). After the concentration measurement, the air in the sachet was newly replaced with air containing 50 ppm aldehyde (formaldehyde), left standing at 25 ° C. for 30 minutes, and the aldehyde (formaldehyde) adsorption concentration was measured with a detector tube. This operation was repeated, and a total of three adsorption amounts were calculated. (See Equation 1.)

  As shown in Table 1, the formaldehyde adsorption amounts of the aldehyde adsorbent A, aldehyde adsorbent B, and aldehyde adsorbent C of the present invention were 0.20 mmol / g, 0.31 mmol / g, and 0.26 mmol / g, respectively. On the other hand, the adsorbents of adsorbent X, adsorbent Y, and activated carbon were 0.11 mmol / g, 0.09 mmol / g, and 0.06 mmol / g, respectively.

Test Example 2 Acetaldehyde Adsorption Test Aldehyde adsorbent A, aldehyde adsorbent B, aldehyde adsorbent C, adsorbent X, adsorbent obtained in Production Example 1, Production Example 2, Production Example 3, Comparative Example 1, and Comparative Example 2 Y, activated carbon (average pore diameter: 0.8 nm, specific surface area: 800 m ² / g, pore volume: 0.4 cm ² / g, amino group and / or imino group content: 0 mmol / g) An adsorption test was performed.
(Aldehyde adsorption test)
100 mg of aldehyde adsorbent was put into an “odor bag” (bag capacity: 3 L, bag size: 250 × 250 mm, material: polyester film / manufactured by ASONE Corporation) containing 2.5 L of air containing 50 ppm aldehyde (acetaldehyde), After standing at 25 ° C. for 30 minutes, the aldehyde (acetaldehyde) concentration in the head space in the odor bag was measured with a gas detector tube (manufactured by Gastec Co., Ltd.). After the concentration measurement, the air in the sachet was newly replaced with air containing 50 ppm aldehyde (acetaldehyde), allowed to stand at 25 ° C. for 30 minutes, and then the aldehyde (acetaldehyde) adsorption concentration was measured with a detector tube. This operation was repeated, and a total of three adsorption amounts were calculated. (See Equation 1.)

As shown in Table 2, the acetaldehyde adsorption amounts of the aldehyde adsorbent A, aldehyde adsorbent B, and aldehyde adsorbent C of the present invention were 0.12 mmol / g, 0.17 mmol / g, and 0.15 mmol / g, respectively. On the other hand, the adsorbents of adsorbent X, adsorbent Y, and activated carbon were 0.06 mmol / g, 0.04 mmol / g, and 0.03 mmol / g, respectively.
Test Example 3 Propionaldehyde Adsorption Test Aldehyde adsorbent A, aldehyde adsorbent B, aldehyde adsorbent C, adsorbent X, adsorption obtained in Production Example 1, Production Example 2, Production Example 3, Comparative Example 1 and Comparative Example 2 Agent Y, activated carbon (average pore diameter: 0.8 nm, specific surface area: 800 m ² / g, pore volume: 0.4 cm ² / g, amino group and / or imino group content: 0 mmol / g) An aldehyde adsorption test was conducted.
(Aldehyde adsorption test)
100 mg of aldehyde adsorbent was put into a “smell bag” (bag capacity: 3 L, bag size: 250 × 250 mm, material: polyester film / manufactured by ASONE Corporation) containing 2.5 L of air containing 50 ppm of aldehyde (propionaldehyde). After standing at 25 ° C. for 30 minutes, the aldehyde (propionaldehyde) concentration in the head space in the odor bag was measured with a gas detector tube (manufactured by Gastec Co., Ltd.). After the concentration measurement, the air in the sachet was newly replaced with air containing 50 ppm aldehyde (propionaldehyde), allowed to stand at 25 ° C. for 30 minutes, and then the aldehyde (propionaldehyde) adsorption concentration was measured with a detector tube. This operation was repeated, and a total of three adsorption amounts were calculated. (See Equation 1)

As shown in Table 3, the propionaldehyde adsorption amounts of the aldehyde adsorbent A, aldehyde adsorbent B, and aldehyde adsorbent C of the present invention were 0.08 mmol / g, 0.13 mmol / g, and 0.12 mmol / g, respectively. . On the other hand, the adsorbents of adsorbent X, adsorbent Y, and activated carbon were 0.04 mmol / g, 0.03 mmol / g, and 0.02 mmol / g, respectively.
Test Example Butyraldehyde Adsorption Test Aldehyde adsorbent A, aldehyde adsorbent B, aldehyde adsorbent C, adsorbent X, adsorbent obtained in Production Example 1, Production Example 2, Production Example 3, Comparative Example 1 and Comparative Example 2 Y, activated carbon (average pore diameter: 0.8 nm, specific surface area: 800 m ² / g, pore volume: 0.4 cm ² / g, amino group and / or imino group content: 0 mmol / g) An adsorption test was performed.
(Aldehyde adsorption test)
100 mg of aldehyde adsorbent was put into a “smell bag” (bag capacity: 3 L, bag size: 250 × 250 mm, material: polyester film / As One Co., Ltd.) containing 2.5 L of air containing 50 ppm aldehyde (butyraldehyde). After standing at 25 ° C. for 30 minutes, the aldehyde (butyraldehyde) concentration in the head space in the odor bag was measured with a gas detector tube (manufactured by Gastec Co., Ltd.). After the concentration measurement, the air in the odor bag was newly replaced with air containing 50 ppm aldehyde (butyraldehyde), allowed to stand at 25 ° C. for 30 minutes, and then the aldehyde (butyraldehyde) adsorption concentration was measured with a detector tube. This operation was repeated, and a total of three adsorption amounts were calculated. (See Equation 1.)

As shown in Table 4, the butyraldehyde adsorption amounts of the aldehyde adsorbent A, aldehyde adsorbent B, and aldehyde adsorbent C of the present invention were 0.07 mmol / g, 0.09 mmol / g, and 0.08 M / g, respectively. . On the other hand, the adsorbents of adsorbent X, adsorbent Y and activated carbon were 0.03 mmol / g, 0.02 mmol / g and 0.01 mmol / g, respectively.
Test Example 5 Crotonaldehyde Adsorption Test Aldehyde adsorbent A, aldehyde adsorbent B, aldehyde adsorbent C, adsorbent X, adsorption obtained in Production Example 1, Production Example 2, Production Example 3, Comparative Example 1 and Comparative Example 2 Agent, activated carbon (average pore diameter: 0.8 nm, specific surface area: 800 m ² / g, pore volume: 0.4 cm ² / g, amino group and / or imino group content: 0 mmol / g) An aldehyde adsorption test was conducted.
(Aldehyde adsorption test)
100 mg of aldehyde adsorbent was put into a “smell bag” (bag capacity: 3 L, bag size: 250 × 250 mm, material: polyester film / Azuwan Co., Ltd.) containing 2.5 L of air containing 50 ppm aldehyde (crotonaldehyde). After standing at 25 ° C. for 30 minutes, the aldehyde (crotonaldehyde) concentration in the head space in the odor bag was measured with a gas detector tube (manufactured by Gastec Co., Ltd.). After the concentration measurement, the air in the odor bag was newly replaced with air containing 50 ppm aldehyde (crotonaldehyde), allowed to stand at 25 ° C. for 30 minutes, and then the aldehyde (crotonaldehyde) adsorption concentration was measured with a detector tube. This operation was repeated, and a total of three adsorption amounts were calculated. (See Equation 1)

  As shown in Table 5, the crotonaldehyde adsorption amounts of the aldehyde adsorbent A, aldehyde adsorbent B, and acetaldehyde adsorbent C of the present invention were 0.04 mmol / g, 0.06 mmol / g, and 0.05 mmol / g, respectively. . On the other hand, the adsorbents of adsorbent X, adsorbent Y, and activated carbon were 0.02 mmol / g, 0.01 mmol / g, and 0.006 mmol / g, respectively.

  The aldehyde adsorbent of the present invention makes it possible to adsorb and remove aldehydes which are not excellent in the past, and its industrial utility value is great.

FIG. 1 is a view showing an X-ray diffraction pattern of the aldehyde adsorbent A. FIG. 2 is a view showing an X-ray diffraction pattern of the aldehyde adsorbent B. FIG. 3 is a view showing an X-ray diffraction pattern of the aldehyde adsorbent C. FIG. 4 is a diagram showing an X-ray diffraction pattern of the adsorbent X. FIG. 5 is a diagram showing an X-ray diffraction pattern of the adsorbent Y.

Claims (2)

Containing a porous silica material having an average pore diameter of more than 1 nm and a compound having an amino group and / or imino group of 1.0 to 20 mmol / g (aldehyde adsorbent), at least one at a position where the d interval is more than 2 nm Aldehyde adsorbent having X-ray diffraction pattern with peaks An aldehyde adsorbent produced by mixing a porous silica and a compound having an amino group and / or an imino group in a non-aqueous solvent

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