KR100610468B1 - Adsorbent composition of harmful gas flowing into the inside of a car - Google Patents

Abstract

The present invention relates to an adsorbent composition capable of absorbing and removing harmful gases introduced into an automobile. The harmful gas adsorbent composition introduced into an automobile according to the present invention includes (a) a spherical hollow core portion and mesoporous carbon. A nano carbon ball made of a shell part and having at least one deodorant selected from the group consisting of transition metals, transition metal oxides and alkali metal salts on the carbon shell part; And (b) a zeolite having a molar ratio of SiO ₂ / Al ₂ O ₃ having an ion species of NH 4 ⁺ type of 20 to 300 and carrying a quaternary ammonium salt, wherein the content ratio of the zeolite: nanocarbon ball is 1 to 1 by weight. 3: 3-8. The adsorbent composition described above may be usefully used in an air conditioner or cabin filter of an automobile because it absorbs and efficiently removes major harmful gases introduced into the vehicle, such as aldehyde, ammonia, trimethylamine, acetic acid, and the like.

Nano Carbon Ball, Zeolite, Adsorbent

Description

Adsorbent composition of harmful gas flowing into the inside of a car}

The present invention relates to an adsorbent composition capable of adsorbing and removing major harmful gases introduced into an automobile.

Cars are essential to modern people. As pollution increases, efforts are being made to keep the interior of the car in a more pleasant environment. There are three main sources of harmful gas flowing into the vehicle. Firstly, harmful gases volatilized from materials such as paint adhesives used in manufacturing cars, secondly, substances emitted from passengers, including drivers, and their favorite products (eg cigarettes), and thirdly, substances coming from outside when driving a car. . Therefore, there may be thousands of gases as the harmful gases flowing into the vehicle, but representative examples of the harmful gases include aldehydes such as acetaldehyde and formaldehyde, acetic acid, trimethylamine, and ammonia.

As an adsorbent that can remove harmful gases, for example, activated carbon impregnated with a deodorant substance (see Korean Patent Publication No. 1999-80808). In addition, an adsorbent (see International Application No. PCT / KR2003 / 1149) impregnated with a deodorizing substance such as transition metal to a nano carbon ball composed of a spherical hollow core part and a mesoporous carbon shell part, or an ion species of NH 4 ⁺ type and SiO ₂ A molar ratio of / Al ₂ O ₃ is in a predetermined range and a zeolite carrying a quaternary ammonium salt (see Korean Patent Laid-Open No. 2001-78018) can be used.

However, activated carbon impregnated with a deodorant does not have a great ability to remove harmful gases, and nano carbon balls with a deodorant have a small ability to remove aldehydes. In addition, the above-described zeolite has a large removal ability to aldehydes, but a small removal ability to other harmful gases introduced into the vehicle.

Therefore, there is a demand for developing an adsorbent having excellent removal ability against all major harmful gases introduced into the vehicle.

The present invention has been made to solve the problems of the prior art, to provide an adsorbent composition that can be efficiently removed by adsorbing the major harmful gases introduced into the vehicle, such as aldehyde, ammonia, trimethylamine, acetic acid.

In order to solve the technical problem as described above, the harmful gas adsorbent composition introduced into the vehicle of the present invention comprises (a) a spherical hollow core portion and a mesoporous carbon shell portion, the transition metal, transition metal in the carbon shell portion Nano carbon balls to which at least one deodorant selected from the group consisting of an oxide and an alkali metal salt is attached; And (b) a zeolite having a molar ratio of SiO ₂ / Al ₂ O ₃ having an ion species of NH 4 ⁺ type of 20 to 300 and carrying a quaternary ammonium salt, wherein the content ratio of the zeolite: nanocarbon ball is 1 to 1 by weight. 3: 3-8.

In addition, the present invention (a) is composed of a spherical hollow core portion and a mesoporous carbon shell portion, nano carbon having any one or more deodorant selected from the group consisting of transition metal, transition metal oxide and alkali metal salt in the carbon shell portion Carbon ball; And (b) a zeolite in which the ionic species is NH4 ⁺ type, the molar ratio of SiO ₂ / Al ₂ O ₃ is 20 to 300, and the quaternary ammonium salt is supported (c) transition metal, transition metal oxide and alkali metal salt. It includes activated carbon impregnated with any one or more deodorant, the content ratio of the zeolite: nano carbon ball: activated carbon provides a 1 to 3: 3 to 8: 3 to 8 by weight ratio of the harmful gas adsorbent composition.

In the adsorbent composition of the present invention, the particle diameter of the hollow core portion of the nano carbon ball is preferably 10 to 1,000 nm, the thickness of the carbon shell portion is 10 to 500 nm, and it is preferable that the zeolite has a β-crystal structure.

Hereinafter, the present invention will be described in detail.

As mentioned above, various kinds of adsorbents have the capability of removing harmful gases. However, each of the conventional adsorbents only have a specific type of harmful gas removal ability to remove the major harmful gas flowing into the vehicle, or there is a limit to the harmful gas removal ability.

The inventors have found that the adsorbent composition, in which a specific deodorant-impregnated nano carbon ball and zeolite are mixed at a predetermined ratio, can remove not only all of the major harmful gases flowing into the vehicle above a certain standard, but also the removal ability is increased. The present invention has been completed.

The harmful gas adsorbent composition introduced into the vehicle of the present invention comprises (a) a spherical hollow core portion and a mesoporous carbon shell portion, wherein the carbon shell portion is selected from the group consisting of transition metals, transition metal oxides and alkali metal salts. Nano carbon balls impregnated with at least one deodorant; And (b) a zeolite having a molar ratio of SiO ₂ / Al ₂ O ₃ having an ion species of NH 4 ⁺ type of 20 to 300 and carrying a quaternary ammonium salt, wherein the content ratio of the zeolite: nanocarbon ball is 1 to 1 by weight. 3: 3-8.

The manufacturing method of the above-mentioned deodorizing substance-impregnated nano carbon ball is described in detail in International Application No. PCT / KR2003 / 1149 and incorporated herein by reference. Nano carbon ball is a ball-shaped carbon structure consisting of a hollow core portion and a porous shell portion, which is a shell, wherein a transition metal, a transition metal oxide, an alkali metal salt, or a mixture thereof is attached to the shell portion. It is. The mesoporous pores formed in the shell can not only adsorb various malodor generating substances, but the deodorant substance adhering to the pores of the shell and the inside and outside surfaces chemically adsorbs and destroys the malodor generating substances. In addition, since the odor generating material is collected in the hollow core portion of the nano carbon ball, not only a sufficient contact time is provided between the odor generating material and the deodorizing material attached to the inner surface of the shell, but also the decomposition product decomposed by the deodorizing material. It is possible to prevent secondary pollution caused by being discharged to the outside space.

The transition metal or transition metal oxide that may be attached to the shell portion of the nano carbon ball includes copper (Cu), iron (Fe), manganese (Mn), nickel (Ni), cobalt (Co), silver (Ag), and gold ( Transition metals such as Au), vanadium (V), ruthenium (Ru), titanium (Ti), chromium (Cr), zinc (Zn), palladium (Pd), or oxides thereof. Examples of the alkali metal salts include brominated metals. Sodium (NaBr), sodium iodide (NaI), potassium bromide (KBr), potassium iodide (KI), potassium iodide (KIO ₃ ), and the like, but are not limited thereto. The particle diameter of the hollow core portion or the thickness of the carbon shell portion of the nano carbon ball can be adjusted according to the process conditions, and the preferred particle diameter and thickness are 10 to 1,000 nm and 10 to 500 nm, respectively.

The above-mentioned deodorizing substance-impregnated nano carbon balls are excellent in removing harmful gases such as ammonia, acetic acid, and trimethylamine, but are somewhat inferior in removing aldehydes such as acetaldehyde and formaldehyde. In order to solve this problem, the present inventors mixed zeolites having an ion species of NH 4 ⁺ type, a molar ratio of SiO ₂ / Al ₂ O ₃ of 20 to 300, and a quaternary ammonium salt loaded with the above-described deodorant-impregnated nano carbon balls. For the preparation of such a zeolite, it is described in detail in Korean Patent Laid-Open Publication No. 2001-78018, which is incorporated herein by reference. The crystal structure of zeolite may be Y type, β type, ZSM-5 type, mordenite type, ferrilite type or the like, but it is particularly preferable to use a β type.

The zeolite and the nano carbon ball are mixed in a weight ratio of 1-3: 3-8. The adsorbent composition mixed in the above range was found to remove all of the major harmful gases flowing into the vehicle above a certain standard, and surprisingly, the ability to remove the harmful gases was also found to cause synergy. That is, the removal ability is improved more than the removal ability for each of the harmful gases predicted by the respective adsorbent content, which will be described in more detail with reference to the data of Examples and Comparative Examples to be described later.

To the adsorbent compositions of the deodorizing substance-impregnated nano carbon ball and zeolite of the present invention described above, activated carbon to which the deodorizing substance is impregnated can be further added within the scope of not impairing the object of the present invention. In this case, it is preferable to mix zeolite: nano carbon ball: activated carbon in the weight ratio of 1-3: 3-8: 3-8. The added activated deodorant (transition metal, transition metal oxide, alkali metal salt, etc.) impregnated activated carbon may contribute to uniform mixing of zeolite and deodorant-impregnated nano carbon balls while lowering the production cost of the adsorbent composition.

Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present invention can be modified in many different forms, the scope of the present invention should not be construed as limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

Example 1

Ion species NH4 ⁺ type and, SiO ₂ / Al ₂ O ₃ mole ratio is 30, is tetrapropylammonium particle size β-type zeolite, and a hollow core portion with the bromide as a quaternary ammonium compound of about 250nm and the thickness of the carbon shell about 200 nm and KI-adhered nano carbon ball as a deodorant was mixed according to the ratio shown in Table 1 to prepare an adsorbent composition.

Examples 2 to 10 and Comparative Examples 1 to 8

Adsorbents (compositions) were prepared according to the ingredients and contents shown in Table 1 below. Activated carbon was used as a deodorizing substance impregnated activated carbon treated with KOH solution.

For the adsorbents of the above-described examples and comparative examples, removal rate tests were performed on formaldehyde, acetaldehyde, ammonia, trimethylamine, and acetic acid, which are the main harmful gases introduced into the vehicle, and the results are shown in Table 1 below.

0.2 g of adsorbent powder was placed in an adsorption tube, and a breakthrough point, which is a point at which adsorption and desorption were in equilibrium according to ASTM D 6646 evaluation, was observed. In order to evaluate the adsorption capacity under a certain condition, the mass flow controller was used to pass the flow rate at 60 ml / min, and the concentration detected in the adsorbent was observed over time. The device was designed to allow air to pass through the water trap to maintain a constant humidity. It was. The air passing through the water trap meets the deodorant source and enters into the adsorption tube containing the deodorizing sample in a mixed state and then passes through the analyzer.

division absorbent Weight of adsorbent (g) % Removal performance for each deodorant Acetaldehyde and formaldehyde Acetic acid trimethylamine ammonia Example 1 Beta zeolite: carbon nanoball = 1: 3 0.2 g 73 77 74.5 70 Example 2 Beta Zeolite: Carbon Nanoball = 1: 4 0.2 g 70 80 75 72 Example 3 Beta zeolite: carbon nanoball = 2: 5 0.2 g 75 72 72 67 Example 4 Beta zeolite: carbon nanoballs = 3: 7 0.2 g 76 70 71 64 Example 5 Beta Zeolite: Carbon Nanoball = 3: 8 0.2 g 74 75 74 69 Example 6 Beta zeolite: carbon nanoball: activated carbon = 1: 3: 3 0.2 g 66 71 69 62 Example 7 Beta zeolite: carbon nanoball: activated carbon = 1: 5: 3 0.2 g 65 75 73 66 Example 8 Beta zeolite: carbon nanoball: activated carbon = 2: 5: 3 0.2 g 70 73 70 64 Example 9 Beta zeolite: carbon nanoball: activated carbon = 2: 5: 7 0.2 g 66 68 65 56 Example 10 Beta zeolite: carbon nanoball: activated carbon = 3: 8: 8 0.2 g 69 70 67 60 Comparative Example 1 Beta zeolite: activated carbon = 1: 3 0.2 g 63 43.8 41 44 Comparative Example 2 Beta zeolite: activated carbon = 1: 4 0.2 g 62 44 42 44.6 Comparative Example 3 Beta zeolite: activated carbon = 2: 5 0.2 g 69 42.5 40.8 42.5 Comparative Example 4 Beta zeolite: activated carbon = 3: 7 0.2 g 70 42 40 42 Comparative Example 5 Beta zeolite: activated carbon = 3: 8 0.2 g 68 43.2 41.5 43.1 Comparative Example 6 Nano Carbon Ball 0.2 g 45 85 75 79 Comparative Example 7 Beta zeolite 0.2 g 90 40 40 41 Comparative Example 8 Activated carbon 0.2 g 42 45 43 45

Referring to the results of Table 1, it can be seen that the adsorbent composition of the embodiment in which the zeolite and the nano carbon ball were mixed in a predetermined ratio according to the present invention can remove all of the major harmful gases introduced into the vehicle at a predetermined level or more. . In addition, when the removal performance of each harmful gas is examined, it shows synergism, showing a more improved removal ability than each of the harmful gases predicted according to the amount of mixed zeolite and nano carbon ball. Can be.

As such, it can be seen that the adsorbent composition of the embodiment in which the specific zeolite and the nano carbon ball are mixed in a predetermined ratio according to the present invention can remove all the major harmful gases introduced into the vehicle at a predetermined level or more. In addition, when the removal performance of each harmful gas is examined, it shows synergism by showing an improved removal ability than the removal ability of each harmful gas predicted according to the mixture amount of zeolite and nano carbon ball. have. Therefore, the adsorbent composition of the present invention may be applied to an air conditioner or cabin filter of a vehicle interior, and may be usefully used to keep the interior of a vehicle comfortable.

Claims (4)

(a) a nano carbon ball comprising a spherical hollow core portion and a mesoporous carbon shell portion, to which at least one deodorant selected from the group consisting of transition metals, transition metal oxides and alkali metal salts is attached; And (b) an ionic species of type NH 4 ⁺ , comprising a zeolite having a molar ratio of SiO ₂ / Al ₂ O ₃ of 20 to 300 and carrying a quaternary ammonium salt, Toxic gas adsorbent composition introduced into the vehicle, characterized in that the content ratio of the zeolite: nano carbon ball is mixed in a weight ratio of 1 to 3: 3 to 8. (a) a nano carbon ball comprising a spherical hollow core portion and a mesoporous carbon shell portion, to which at least one deodorant selected from the group consisting of transition metals, transition metal oxides and alkali metal salts is attached; And (b) a zeolite in which the ionic species is NH4 ⁺ type, the molar ratio of SiO ₂ / Al ₂ O ₃ is 20 to 300, and the quaternary ammonium salt is supported; (c) activated carbon impregnated with at least one deodorant selected from the group consisting of transition metals, transition metal oxides and alkali metal salts, The zeolite: nano carbon ball: activated carbon is a harmful gas adsorbent composition introduced into the vehicle, characterized in that the content ratio of 1 to 3: 3 to 8: 3 to 8 by weight ratio. 3. The harmful gas adsorbent composition of claim 1 or 2, wherein the hollow core portion has a particle diameter of 10 to 1,000 nm and a carbon shell portion has a thickness of 10 to 500 nm. The harmful gas adsorbent composition according to claim 1 or 2, wherein the zeolite has a β-type crystal structure.