KR100693363B1 - Adsorbents for Removing Aldehyde Compounds - Google Patents

Abstract

The present invention relates to an adsorbent for removing an aldehyde compound, and more particularly, to a porous solid carrier, metals such as platinum (Pt), palladium (Pd), silver (Ag), and rhodium (Rh), which are main active ingredients, Compounds such as KI, KIO ₃ , NH ₄ I and NH ₄ IO ₃ , which are active ingredients, are simultaneously supported in a certain component ratio, thereby improving adsorption performance and adsorption retention compared to the prior art, and in particular, formaldehyde, acetaldehyde, propionaldehyde, etc. The present invention relates to an adsorbent for removing aldehyde compounds, which can be used as a material in various fields from indoor air purification to pollution-generating industrial sites due to its excellent effect when applied to lower aldehyde compounds.

Solid carrier, main active ingredient, auxiliary active ingredient, aldehyde compound, adsorbent

Description

Adsorbents for Removing Aldehyde Compounds

1 shows an apparatus for measuring activity of a catalyst according to the present invention.

[Description of main part of drawing]

1: Aldehyde Cylinder 2: Air Cylinder 3: MFC

4: constant temperature bubble port 5: constant temperature fixed adsorption tower

6: gas chromatograph 7: three-way valve

8: MFC controller 9: Temperature controller 10: Vent

The present invention relates to an adsorbent for removing an aldehyde compound, and more particularly, to a porous solid carrier, metals such as platinum (Pt), palladium (Pd), silver (Ag), and rhodium (Rh), which are main active ingredients, Compounds such as KI, KIO ₃ , NH ₄ I and NH ₄ IO ₃ , which are active ingredients, are simultaneously supported in a certain component ratio, thereby improving adsorption performance and adsorption retention compared to the prior art, in particular, such as formaldehyde, acetaldehyde, propionaldehyde, etc. The present invention relates to an adsorbent for removing aldehyde compounds, which can be used as a material in various fields from indoor air purification to pollution-generating industrial sites due to its excellent effect when applied to lower aldehyde compounds.

There are several ways to selectively remove a particular gas, but it is most common to use an adsorbent and a catalyst to remove it.

In order to remove toxic organic compounds at room temperature, it is preferable to use an adsorbent, and as the adsorbent, activated carbon, zeolite, layered compounds and the like are commonly used. However, these have a disadvantage in that the adsorption capacity is limited in itself, so that the adsorption capacity is reduced or extinguished after a certain time, and that it is not easy to reuse. In order to overcome these disadvantages, studies on improving the adsorption capacity for a specific gas by administering a certain amount of the active ingredient to a solid carrier, and various examples of using the same are known.

On the other hand, when using a catalyst has the advantage that can be recycled by introducing a number of active metal to the carrier can be recycled several times, there is a problem that the core technology development is not easy. In order to remove an organic compound such as aldehyde by using a catalyst, it is required to heat the temperature to at least 200 ° C. or higher in air, and it is known that no catalytic reaction occurs at room temperature.

In general, expensive noble metals are used as active metals to purify toxic gases harmful to humans.However, research on the technology of minimizing the use of these precious metals or adding supplementary components with precious metals has been conducted due to price competitiveness. The situation is active.

The following is the introduction of several related documents on the development of adsorbents used to remove toxic gases by supporting these active ingredients in solid carriers.

U.S. Patent No. 6,596,909 B2 in the ammonium cation and quaternary ammonium-containing ions, and the ZSM-5 and ferrierite _{(ferrierite) SiO 2 / Al 2} O 3 = 30-190 may be a long period of time the adsorption of formaldehyde and acetaldehyde Suggested material. However, quaternary ammonium ions are expensive, and if the temperature is high, the nitrogen compounds inherent in the material may desorb and cause an unpleasant odor, and the material itself is in the form of powder. There is a possibility. In this case, the inorganic oxide may be used as a suitable carrier, but when the organic compound is introduced as an active ingredient, the inorganic oxide may be desorbed at a high temperature which is unexpected in a real situation and lose its performance.

Japanese Patent No. 3321422 and Japanese Patent Laid-Open No. 2000-140577 relate to an apparatus for removing trace amounts of carbon monoxide, nicotine, acetaldehyde, ammonia and sulfur dioxide present in an enclosed space. The device uses a catalyst in which oxides such as alumina, silica, iron oxide, titania, zirconia and zeolite are supported on metals such as platinum, cerium, palladium, magnesium and titanium to remove carbon monoxide, and activated carbon, to remove aldehydes. Adsorbents such as silica gel and titania are used, cohesive activated carbon adsorbent is used to remove ammonia, and catalysts in which manganese and copper are supported on oxides such as titania, alumina, silica, and zeolite are used to remove sulfur dioxide. However, these catalysts are capable of removing each toxic gas within a temperature range of 40 to 60 ° C. higher than room temperature, so that a special heating device is required separately.

Japanese Patent Laid-Open Nos. 2000-281998 and 2002-327941 use polyamine-supported silica as an adsorbent to remove acetaldehyde, and International Application No. 91 / 01,175 describes a low temperature oxidation catalyst. It is suggested that oxide catalysts of metals such as iron, manganese, copper, rare earth vanadium, and chromium supported by noble metals can oxidize molecules having a molecular weight of less than 50 at 30 ° C. At this time, it is claimed that oxygen-deficient sites can be introduced into the oxide even by careful reduction treatment at room temperature. However, in order to create oxygen-deficient sites in the metal oxide, it is known that the reduction should be performed at a temperature of at least 400 ° C or higher. In practice it is expected to be very difficult.

According to other published literature [Clay Science 8, 195-209 (1992)], adsorbents made by combining 2-aminobenzoic acid with a layered inorganic oxide such as sepiolite, etc., are compared with simple sepiolite. Therefore, it has been reported that the adsorption of acetaldehyde in the atmosphere of high relative humidity is greatly improved. However, such an adsorbent is also undesirable since there is a possibility that 2-aminobenzoic acid may desorb and become a third toxic gas in a high temperature atmosphere which is unexpected in actual situations.

According to Japanese Patent No. 2004-149173, platinum (Pt), rhodium (Rh), rhodium (Ru), palladium (Pd) and silver (Ag) are used for inorganic porous carriers such as zeolite, silica, activated carbon, and the like. Metal fine particles and alkyl benzene sulfonates, alkyl naphthalene sulfonates, polyoxyalkyl ether sulfates, polyoxyethylene alkyl phenyl ether phosphates, one selected from gold (Au), cobalt (Co), nickel (Ni) and iron (Fe) It is proposed a catalyst comprising one anionic surfactant selected from among. However, not only the activity decreases as the reaction time passes, but it is not easy to regenerate the catalyst once deactivated.

Japanese Patent Nos. 2004-9026 and 2004-9000 show that an adsorbent carrying benzenesulfonic acid on a porous inorganic carrier such as activated carbon, zeolite, bentonite, and the like has excellent lower aliphatic aldehyde removal performance. However, it is difficult to find a solvent capable of easily dissolving benzenesulfonic acid, so that it is not easy to carry a desired amount of benzenesulfonic acid.

Japanese Patent Application Laid-Open No. 56-53744 discloses an adsorbent adhering aniline to activated carbon, and Japanese Patent Application Laid-Open Publication No. 59-186641 discloses an adsorbent adhering polyethylene imine to activated carbon; and Japanese Patent Application Laid-Open No. 60-132645 discloses aniline, toluidine and benzyl in clay minerals. Adsorbents carrying amines or salts thereof have been proposed. However, in the conventional adsorbents, adsorbents containing aniline, hydrochloric acid hydroxylamine, sulfate sulfate amine, polyethyleneimine, toluidine, benzylimine, etc., are easily oxidized in the air, thereby degrading adsorption performance. There is a problem with use or storage.

U.S. Patent No. 6,492,298 introduces a method for preparing a catalyst for oxidation reaction that exhibits performance at room temperature, and a catalyst made by supporting precious metals on metal oxides such as ceria and zirconia having oxygen-deficient sites by reduction is included in the air. Toxic gases such as CO, NOx, ethylene, formaldehyde, trimethylamine, methylmercaptan and acetaldehyde can be purified at 25 ° C.

Accordingly, the present inventors have deeply studied the performance and cost-effectiveness of the conventional adsorbent, and in particular, have tried to develop a novel solid-state adsorbent having excellent adsorption capacity to the aldehyde compound. As a result, a certain amount of at least one metal selected from platinum (Pt), palladium (Pd), silver (Ag), and rhodium (Rh) is used as a main active ingredient in a porous solid carrier, and specific KI, KIO ₃ , NH _By further using at least one compound selected from ₄ I and NH ₄ IO ₃ , the economic loss in the case of using the above-mentioned main active ingredient alone is improved by the introduction of the auxiliary active ingredient, and the main active ingredient is highly dispersed in the solid carrier. The present invention was completed to improve the adsorption performance and adsorption holding power for lower aldehyde compounds, and found that the amount of the main active ingredient relative to that of the prior art was lowered, so that the economic efficiency was excellent.

Accordingly, an object of the present invention is to provide an adsorbent for removing aldehyde compounds having improved adsorption capacity, adsorption holding power and economic efficiency.

The present invention is a porous solid carrier,

At least one metal selected from platinum (Pt), palladium (Pd), silver (Ag) and rhodium (Rh) as the main active ingredient,

The adsorbent for aldehyde compound removal is formed by simultaneously supporting at least one compound selected from KI, KIO ₃ , NH ₄ I and NH ₄ IO ₃ as an auxiliary active ingredient.

Hereinafter, the present invention will be described in detail.

The present invention is a new adsorbent that can remove lower aldehyde compounds such as gaseous formaldehyde, acetaldehyde and propionaldehyde at room temperature, and simultaneously supports the main active ingredient, which is a specific metal component, and a specific auxiliary active ingredient in a certain ratio on a porous carrier. The present invention relates to an adsorbent for removing aldehyde compounds.

That is, the present invention is characterized by the composition of the active ingredient, the main active ingredient is among the various metal components commonly used in the art among platinum (Pt), palladium (Pd), silver (Ag) and rhodium (Rh) By using at least one selected metal component, and at the same time as an auxiliary active ingredient, the dispersibility of the main active ingredient to the solid carrier and the synergistic action of the active ingredients significantly improve the adsorption performance of the aldehyde compound, It is characterized by the selection and use of one or more compounds selected from specific KI, KIO ₃ , NH ₄ I and NH ₄ IO _{3 which} also have an excellent effect on maintenance.

Looking at the adsorbent for removing aldehyde compounds according to the present invention in more detail.

Porous carrier is generally used in the manufacture of the adsorbent in the art, but is not particularly limited, specifically, for example, in activated carbon, alumina, synthetic zeolite, natural zeolite, zirconia, titania, silica, inorganic oxide-based layered compound and mixtures thereof You can use the selected one.

The present invention is characterized by the technical configuration of the mixed use of a specific main active ingredient and auxiliary active ingredient in a certain ratio as the active ingredient supported on the porous carrier.

The main active ingredient is a metal component commonly used in the art, in particular, it can be easily removed by the effective adsorption of toxic gas, among platinum (Pt), palladium (Pd), silver (Ag) and rhodium (Rh) One or more selected metal components are selected and used.
In this case, it is preferable to use a water-soluble salt such as nitrate, acetate, etc., because the metal is effectively dispersed in the carrier by effectively contacting the metal ions dissolved in water with the carrier. When insoluble salts are used, there is a technical difficulty in making the metal component highly dispersed in the carrier.

As the auxiliary active ingredient, the main active ingredient can be highly dispersed in the solid carrier, which has the property of improving the adsorption performance, and exhibits synergistic effects with the main active ingredient, KI, KIO ₃ , NH ₄ I and One or more compounds selected from NH ₄ IO ₃ are used.

The main active ingredient and the auxiliary active ingredient maintain a weight ratio of 0.05 to 0.1: 1, and when the content of the main active ingredient is less than 0.05 weight ratio, the adsorption capacity is low and when the content exceeds 0.1 weight ratio, the adsorption capacity is excellent. However, it is desirable to maintain the above range because of uneconomical problems.

The active ingredient is supported by 1.0 to 10.0% by weight with respect to the porous carrier. When the supported amount is less than 1.0% by weight, the adsorption capacity is low and when the amount exceeds 10.0% by weight, the technique of high dispersion of the active ingredient is not easy. It will affect the adsorption capacity.

On the other hand, the manufacturing method of the adsorbent for removing an aldehyde compound according to the present invention will be described in detail.

First, impurities, dust and the like present in the solid carrier are removed. This is not particularly limited by the conventional method, but in the present invention, the solid carrier is washed with distilled water once or twice and then dried in a temperature range of 100 to 120 ° C. for about 24 hours.

In order to further improve the washing power of the solid carrier, the solid carrier and the acid solution washed above are mixed at a volume ratio of 1: 1 to 2, left at room temperature for 8 to 12 hours or more, and washed with distilled water once or twice. As the acid solution, a solution obtained by mixing concentrated nitric acid or sulfuric acid with distilled water in a volume ratio of 1: 1.

Next, the auxiliary active ingredient solution having the same volume as the solid carrier is mixed and stirred with the solid carrier and dried at 100 to 120 ° C. for about 8 to 12 hours.

The auxiliary active ingredient is quantified in the range of 0.5 to 5.0% by weight based on the solid carrier, and then a solution dissolved in distilled water having the same volume is used.

Thereafter, the same volume of the main active ingredient solution as the solid carrier containing the auxiliary active ingredient is mixed and stirred, followed by drying at about 100 to 120 ° C. for about 8 to 10 hours to prepare an adsorbent.

The main active ingredient is quantified in the range of 0.1 to 3.0% by weight based on the solid carrier, and then a solution dissolved in distilled water having the same volume is used.

The active ingredient is preferably carried by the secondary active ingredient and the main active ingredient in a solid carrier sequentially, if the order is changed, there is a problem of being damaged by the functional auxiliary active ingredient of the main active ingredient, weakening the adsorption power of the present invention It is better to keep the same order.

The adsorbent prepared in this way is capable of effectively removing lower aldehyde compounds such as formaldehyde, acetaldehyde, propionaldehyde, etc. by dispersing the main active ingredient and the auxiliary active ingredient on the carrier.

Hereinafter, the present invention will be described in more detail with reference to the following examples, which are not intended to limit the present invention.

Example 1

As shown in Table 1 below, the activated carbon carrier, which was not treated with acid, was loaded with 3.0 wt% of KI and 2.0 wt% of KIO ₃ as auxiliary active ingredients, and left to dry for 24 hours. An adsorbent was prepared by supporting 0.03% by weight of Pt and 0.07% by weight of Pd on a carrier on which the auxiliary active ingredient was carried out, followed by stagnation for 24 hours.

Example 2

As in Example 1, but as shown in the following Table 1, using 2.0 wt% KIO ₃ and 3.0 wt% NH ₄ I as the auxiliary active ingredient, 0.3 wt% Pt and Ag 0.2 as the main active ingredient The adsorbents were prepared using weight percent.

Example 3

As in Example 1, but as shown in the following Table 1, using the NH ₄ I 4.0 wt% and NH ₄ IO ₃ 1.0 wt% as the auxiliary active ingredient, 1.2 wt% Ag and the main active ingredient Adsorbents were prepared using 1.0 wt% Rh.

Example 4

As in Example 1, but as shown in Table 1, 1.0 wt% KIO ₃ and 4.0 wt% NH ₄ IO ₃ is used as the auxiliary active ingredient, 0.2 wt% Pd and Rh as the main active ingredient An adsorbent was prepared using an activated carbon carrier using 0.1 wt% and treated with an acid as the carrier.

Example 5

In the same manner as in Example 1, as shown in the following Table 1, 2.0 wt% of KI and 0.5 wt% of NH ₄ I are used as the auxiliary active ingredients, and 0.2 wt% of Pt and 0.3 wt% of Ag are the main active ingredients. The adsorbent was prepared using an activated carbon carrier treated with an acid as a carrier.

Comparative Example 1

As shown in Table 1, only the activated carbon carrier itself, which was not treated with acid, was washed with distilled water 1 to 2 times and dried to prepare an adsorbent.

Comparative Example 2

As shown in Table 1, only the activated carbon carrier itself treated with acid was washed with distilled water 1 to 2 times and dried.

Comparative Example 3

As in Example 1, but as shown in Table 1, the adsorbent was prepared using KI 3.0 wt% and KIO ₃ 2.0 wt% as a secondary active ingredient excluding the main active ingredient.

Comparative Example 4

As in Example 1, but as shown in the following Table 1, the activated carbon carrier treated with acid using 2.0 wt% of KIO ₃ and 3.0 wt% of NH ₄ I as auxiliary active ingredients, excluding the main active ingredient Was used to prepare the adsorbent.

Comparative Example 5

As in Example 1, but as shown in Table 1, the adsorbent was prepared using 0.3% by weight of Pd and 0.2% by weight of Ag as the main active ingredient excluding the auxiliary active ingredient.

The types and amounts of the carriers and the active ingredients used in Examples 1 to 5 and Comparative Examples 1 to 5 are summarized in Table 1 below.

division Active ingredient (% by weight) Main active ingredient Auxiliary active ingredients Pt Pd Ag Rh KI KIO ₃ NH ₄ I NH ₄ IO ₃ Example 1 0.03 0.07 - - 3.0 2.0 - - Example 2 - 0.3 0.2 - - 2.0 3.0 - Example 3 - - 1.2 1.0 - - 4.0 1.0 Example 4 - 0.2 - 0.1 - 1.0 - 4.0 Example 5 0.2 0.3 - 2.0 - 0.5 - Comparative Example 1 - - - - - - - Comparative Example 2 - - - - - - - Comparative Example 3 - - - 3.0 2.0 - - Comparative Example 4 - - - - 2.0 3.0 - Comparative Example 5 - 0.3 0.2 - - - - -

In order to measure the activity of the catalyst prepared by the preparation method as described above, it was measured by the catalytic activity measuring apparatus of FIG. The catalytic activity measuring device is configured by organically connecting three parts, such as a toxic gas supply device, a vertical reaction vessel, and an activity evaluation device.

In Fig. 1, toxic gases such as acetaldehyde and ammonia supplied from the gas cylinder 1 are respectively flowed out, mixed with oxygen 2 and diluted, and the diluted mixed gas passes through the flow regulator 3 and is fixed bed. It is configured to be introduced directly into the reactor (5), or after passing through the water (5) to enter the fixed bed reactor (5). That is, it is introduced into a fixed bed reactor with water vapor saturated at room temperature and saturated, or a dry mixed gas is directly introduced into a vertical reactor. At this time, the amount and speed of each gas was controlled by the flow controller (3), the fixed bed reactor (5) was made of Pyrex glass 50 cm long, 1.6 cm outer diameter size.

The adsorbent was mounted in the middle of the reactor in the form of granules, and the mixed gas was adsorbed by the active ingredients supported on the carrier while passing through the mounted adsorbent bed, and then quantified by a detector.

At this time, formaldehyde, acetaldehyde and propionaldehyde concentration was quantified using a gas chromatograph.

Experimental Example

In order to evaluate the performance of the adsorbents prepared in Examples 1 to 5 and Comparative Examples 1 to 5, the adsorption performance was measured using the activity measuring device shown in FIG. 1.

The amount of adsorbent used for measuring the adsorption performance of the material was filled with 1 g each, the gas flow rate was 100 cc / min, the adsorption reaction was carried out at 20 ~ 25 ℃. In the performance evaluation for formaldehyde, the steam passed through the formaldehyde 38% aqueous solution was diluted with the air supplied from the air cylinder (2) in a constant temperature bubble port as in (4), and used to adjust the injection concentration to 100 ppm. . In the performance evaluation of acetaldehyde, it was used by adjusting the injection concentration to 10,000 ppm by diluting it with air from the 30% acetaldehyde gas supplied from the cylinder (1).

The adsorption performances prepared in Examples 1 to 5 and Comparative Examples 1 to 5 were measured, and the results are shown in Table 2 below.

division Formaldehyde Acetaldehyde Concentration change over time (ppm) 0 minutes (injection concentration) 60 mins 150 minutes 0 minutes (injection concentration) 20 minutes 40 mins Example 1 100 0 0 10,000 0 0 Example 2 100 0 0 10,000 0 0 Example 3 100 0 0 10,000 0 0 Example 4 100 0 0 10,000 0 0 Example 5 100 0 0 10,000 0 0 Comparative Example 1 100 100 100 10,000 10,000 10,000 Comparative Example 2 100 0 33 10,000 0 2,300 Comparative Example 3 100 0 100 10,000 2,000 4,600 Comparative Example 4 100 0 47 10,000 0 3,400 Comparative Example 5 100 0 35 10,000 3,800 8,100

As shown in Table 2, it can be seen that the adsorbents of Examples 1 to 5 simultaneously containing the specific main active ingredient and the auxiliary active ingredient according to the present onset have better adsorption performance of aldehydes than Comparative Examples 1 to 5. there was. Specifically, Examples 1 to 5 show that formaldehyde and acetaldehyde maintain their performance for at least 150 and 40 minutes, respectively, while exhibiting 100% adsorption performance within 60 minutes and 20 minutes, respectively.

On the other hand, in the case of Comparative Examples 1 to 5, it was observed that the initial adsorption performance was excellent, but it did not exhibit the adsorption performance within a short time, and also it is not preferable in terms of maintaining the adsorption performance, it shows that it does not satisfy the function as the adsorbent.

As described above, the adsorbent in which the auxiliary active ingredient and the main active ingredient are sequentially supported on the solid carrier according to the present invention has excellent fast adsorption performance and retaining ability for lower aldehyde compounds, and generates pollution from indoor air purification. It can be used as a material for various industrial fields up to industrial sites.

Claims (7)

In a porous solid carrier selected from activated carbon, alumina, synthetic zeolite, natural zeolite, zirconia, titania, silica, inorganic oxide layered compounds and mixtures thereof, At least one metal selected from platinum (Pt), palladium (Pd), silver (Ag) and rhodium (Rh) as the main active ingredient, and KI, KIO ₃ , NH ₄ I and NH ₄ IO ₃ selected as the auxiliary active ingredient At least one compound is supported at the same time, An adsorbent for removing an aldehyde compound, wherein the main active ingredient and the auxiliary active ingredient are carried in a weight ratio of 0.05 to 0.1: 1. delete The adsorbent for removing an aldehyde compound according to claim 1, wherein the main active ingredient and the auxiliary active ingredient are supported by 1.0 to 10.0 wt% on the porous carrier. The adsorbent for aldehyde compound removal according to claim 1, wherein the main active ingredient is derived from nitrate or acetate of each metal. delete The method of claim 1, wherein the solid carrier Adsorbent for removing aldehyde compounds, characterized in that washed with 20 to 80% by weight of nitric acid or sulfuric acid aqueous solution. The adsorbent for removing aldehyde compounds of claim 1, wherein the aldehyde compound is selected from formaldehyde, acetaldehyde and propionaldehyde.

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