KR20180011920A - Reducing agent for VOCs and bad odor producing materials derived from natural material and preparing method thereof - Google Patents

Abstract

The present invention relates to a natural material-derived reducing agent of volatile organic compounds and bad smell causing materials and a preparation method of the natural material-derived reducing agent. More specifically, the present invention provides a preparation method of a reducing agent of volatile organic compounds and bad smell causing materials using a zeolite-based support, the preparation method comprising the steps of: preparing the zeolite-based support; dissolving one or more metal salts into purified water to prepare an aqueous composite metal oxide solution; dissolving an ammonium salt, urea, adipic acid dihydrazide and a surfactant into purified water to prepare a dipping solution; impregnating the zeolite-based support with the aqueous composite metal oxide solution, and dipping the impregnated zeolite-based support into the dipping solution; and drying, pulverizing and firing the dipped zeolite-based support. The reducing agent of the volatile organic compounds and the bad smell causing materials using the zeolite-based support according to the present invention is used as an adsorption material of a natural composite material-based rear shelf that is one of automobile components such that the reducing agent can efficiently reduce the volatile organic compounds and the bad smell causing materials generated within an automobile cabin.

Description

TECHNICAL FIELD [0001] The present invention relates to a volatile organic compound material derived from a natural material, a smell reducing material reducing agent and a method for producing the same,

The present invention relates to a volatile organic compound material derived from a natural material and a method for producing the same, and more particularly, to a method for reducing a volatile organic compound material and a malodor generating material generated in a vehicle interior by using a zeolite support And a method for producing the same.

Recently, Volatile Organic Compounds (VOCs) have been classified as specific atmospheric hazardous substances due to their large impacts on the human body and ecosystem, and photochemical reactions generate photochemical oxides as secondary pollutants such as ozone . These VOCs are toxic to humans and cause problems such as ozone depletion, global warming, photochemical smog, and odor because they contain many chemicals known to be highly carcinogenic.

Direct effects of VOCs on the human body are known to cause leukemia and central nervous disorder in the case of benzene among volatile organic compounds of aromatic hydrocarbons and it is reported that chromosomal abnormalities are often found in people exposed to very low levels of benzene have. Organic solvents, on the other hand, are toxic in their own right, or these substances contained in them are highly toxic and problematic. The most common organic solvents are aromatic hydrocarbons such as benzene, toluene and xylene. These substances are emitted from various sources. The emission of VOCs in Korea accounts for the largest portion of the total amount of emission from the painting industry, which is 55% Sudan is followed by 28%.

The spoils of the automobile industry to cope with environmental regulations that are stronger and stronger all over the world are showing rapid movements both domestically and internationally. In addition to responding to the regulation of indoor automobile indoor air quality, we recognize the need for comfortable living environment and environmental preservation And the selection of eco-friendly materials by automakers to meet the consumer's eye-level.

Therefore, it is urgent to research and develop a reducing agent for reducing VOCs and odorous substances generated by the use of transportation means such as automobiles, which are closely related to human life.

Korean Patent Publication No. 2013-0069282

It is an object of the present invention to provide a volatile organic compound material and a method for reducing a malodor causing material which can effectively reduce VOCs and odor generating substances generated in an automobile interior and a method for manufacturing the same.

In order to accomplish the above object, the present invention provides a method for producing a zeolite- Preparing a composite metal oxide aqueous solution by dissolving at least one metal salt in purified water; Dissolving an ammonium salt, urea, adipic acid dihydrazide and a surfactant in purified water to prepare a supported solution; Impregnating the composite metal oxide aqueous solution with a zeolite-based support, and then supporting the zeolite-based support in a supported solution; And drying and pulverizing the supported zeolite-based support, followed by calcination, to prepare a volatile organic compound material and a method for manufacturing a reducing agent of a malodor-inducing substance using the zeolite-based support.

Also, the present invention provides a volatile organic compound material and a smell-inducing material reducing agent using the zeolite-based support, which are produced according to the above-described production method.

The present invention also provides an adsorbent material comprising the above-described reducing agent.

The volatile organic compound material and the odor inducing substance reducing agent using the zeolite support according to the present invention are used as the adsorbent material of the rear shelf which is one of the automobile parts based on the natural composite material, The substance and the odor-inducing substance can be efficiently reduced.

1 is a schematic view of the reaction on the adsorptive cleaning agent surface,
2 is a view showing the principle of reduction of other odor-inducing components.

Hereinafter, a volatile organic compound material derived from a natural material of the present invention, a smell reducing material reducing agent and a method for producing the same will be described in detail.

The inventors of the present invention have found that when a reducing agent is being developed and developed, a composite metal oxide aqueous solution and a supporting solution are treated by using a zeolite-based support in place of a conventional support for a reducing agent, It is possible to further improve the abatement efficiency against odor-inducing substances, thereby completing the present invention.

The present invention provides a method for preparing a zeolite-based support comprising: preparing a zeolitic support; Preparing a composite metal oxide aqueous solution by dissolving at least one metal salt in purified water; Dissolving an ammonium salt, urea, adipic acid dihydrazide and a surfactant in purified water to prepare a supported solution; Impregnating the composite metal oxide aqueous solution with a zeolite-based support, and then supporting the zeolite-based support in a supported solution; And drying and pulverizing the supported zeolite-based support, followed by calcination, to prepare a volatile organic compound material and a method for manufacturing a reducing agent of a malodor-inducing substance using the zeolite-based support.

2 shows the reaction mechanism showing the principle of reduction of the other odor-inducing components, which is to secure porosity according to the critical diameter size of VOCs and odor components, VOCs and odorous substances are removed by reacting with the acidic base metal supported on the surface.

The step of preparing the zeolite-based support comprises preparing a first solution by dissolving an alkaline agent and an aluminum source in purified water, preparing a second solution by dissolving an alkaline agent, an aluminum source and a silica source in purified water, Reacting the solution and the second solution at 180 to 240 ° C for 24 to 28 hours, and washing the product and then drying at 100 to 150 ° C for 4 to 8 hours, no.

The alkali agent may be any one selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, and calcium hydroxide, but is not limited thereto.

The aluminum source may be selected from the group consisting of aluminum oxide, aluminum hydroxide, aluminum alkoxide, aluminum trihydrate, aluminum chloride hexahydrate, Nitrate, nitrate, nitrate, nonahydrate, and the like, but is not limited thereto.

The silica source may be any one selected from the group consisting of sodium silicate, ethyl silicate, and tetraethyl orthosilicate, but is not limited thereto.

The metal salt may be at least one selected from the group consisting of copper nitrate (Cu (NO ₃ ) ₂ ), zinc nitrate (Zn (NO ₃ ) ₂ ), iron nitrate (Fe (NO ₃ ) ₂ .6H ₂ O) (NO ₃ ) ₃ .6H ₂ O), manganese nitrate (Mn (NO ₃ ) ₂ ), nickel nitrate (Ni (NO ₃ ) ₂ ), and silver nitrate (AgNO ₃ ) A chloride selected from the group consisting of manganese (MnCl ₂ ) and iron chloride (FeCl ₂ ) and sulfate selected from the group consisting of iron sulfate (FeSO ₄ ), zinc sulfate (ZnSO ₄ ), and cobalt sulfate (CoSO ₄ ) , But is not limited thereto.

The ammonium salt is ammonium sulfate _{((NH 4) 2 SO 4} ), sulfamic acid, ammonium _{(NH 4 OSO 2 NH 2)} , ammonium nitrate (NH ₄ NO _3), and aqueous ammonia at least one selected from the group consisting of (NH ₄ OH) But is not limited thereto.

The surfactant may be any one selected from the group consisting of a nonionic surfactant, a cationic surfactant, and an ionic surfactant, but is not limited thereto.

The nonionic surfactant may be selected from the group consisting of methanol, ethanol, isopropanol, butanol, benzyl alcohol, 1,4-butanediol, 1,3-butanediol, , 1,2-propanediol, 1,3-propanediol, trimethylolpropane, sorbitol, xylitol, glycerin, diglycerin, ethylene glycol, diethylene glycol Ethylene glycol monomethyl ether, ethylene glycol phenyl ether, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, propylene glycol, Propyleneglycol phenyl ether, dibutyl diglycol, 3-methyl-3-methoxybutanol, 2- (2-butoxyethoxy) ethanol, polyoxyethylene alkylether, Polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty alcohol, and Lee oxy may be any one selected from the group consisting of polyoxyethylene alkyl phenyl emitter, without being limited thereto.

The cationic surfactant is selected from the group consisting of Cetyltrimethyl ammonium bromide, Hexadecyl trimethyl ammonium bromide, Cetyl trimethylammonium chloride, Cetylpyridinium chloride, Benzalkonium chloride, But are not limited to, benzalkonium chloride, benzethonium chloride, and dioctadecyldimethylammonium bromide. The term " benzalkonium chloride "

The amphoteric surfactant may be any one selected from the group consisting of acetate, imidazole, betaine, phosphatem, and derivatives thereof, It is not.

The supported zeolite odor-reducing support is dried, pulverized and then sintered. The supported zeolite odor-reducing support is dried at 90 to 110 ° C, pulverized to have an average particle size of 5 to 10 μm, And may be fired at 500 DEG C for 3 to 6 hours, but is not limited thereto.

Also, the present invention provides a volatile organic compound material and a smell-inducing material reducing agent using the zeolite-based support, which are produced according to the above-described production method.

The present invention also provides an adsorbent material comprising the above-described reducing agent.

The adsorbent material may include 3 to 10 parts by weight of a reducing agent for 100 parts by weight of adsorbent material, but is not limited thereto.

The adsorbent material may be used as an adsorbent material of a rear shelf part using a natural composite material, but is not limited thereto.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited by these examples.

<Example 1> Production of a volatile organic compound material derived from natural materials and a smell reducing substance reducing agent

1. Preparation of zeolite-based support

11.8 g of sodium hydroxide and 1.2 g of aluminum oxide were added to 100 mL of purified water and completely dissolved to prepare a first mixed solution. To 200 mL of purified water, sodium hydroxide 16 g, aluminum oxide 1.2 g of sodium silicate and 96 g of sodium silicate were added and completely dissolved to prepare a second mixed solution. The first mixed solution and the second mixed solution were mixed and reacted at 180 ° C for 24 hours.

After raising the reaction temperature to 100 ° C., the reaction mixture was reacted through an overhead stirrer (IKA, RW 20.n) at a rate of 150 rpm for 3 hours to produce a white composition. When the temperature dropped to room temperature, After washing with 500 mL of water, the product was dried using a dry oven at 130 DEG C for 6 hours to synthesize a zeolite-based support.

2. Manufacturing method of composite metal oxide aqueous solution

0.01 to 0.2 mol of copper nitrate and iron nitrate were added to 1000 g of water in each of copper nitrate, zinc nitrate, iron nitrate, manganese nitrate, nickel nitrate, silver nitrate, manganese chloride, iron chloride, iron sulfate, zinc sulfate and cobalt sulfate The mixture was completely dissolved and stirred for 30 minutes to prepare a mixed metal oxide aqueous solution.

3. Preparation of aqueous solution containing functional groups and odor reducing VOCs and functional groups

50 to 250 g each of ammonium sulfate, urea, ammonium sulfamate, adipic acid dihydrazide, ammonium nitrate, ammonia water, and a surfactant were added to 500 g of water and completely dissolved. The mixture was completely dissolved in an overhead stirrer (IKA, RW 20.n) to prepare a carrier solution which is an aqueous solution constituting the functional group and VOCs and odor reducing functional groups.

4. Supporting compound metal oxide and lipophilic group, VOCs and functional group for odor reduction on a zeolite-based support

The composite metal oxide aqueous solution prepared above was introduced into a reactor equipped with an overhead stirrer (IKA, RW 20.n) and slowly added with 1000 g of zeolite-based VOCs and deodorizing support while stirring continuously, And stabilized by stirring with an overhead stirrer (IKA, RW 20.n) for 30 minutes.

The prepared lipophilic group and odor reduction functional aqueous solution for slow deodorization were slowly added dropwise to the stabilized zeolite-based VOCs and odor-reducing support, and the resulting mixture was stirred for 3 hours to sufficiently support the zeolite-based VOCs and odor-reducing support . At this time, since the viscosity of the reaction mixture was increased due to the sol-gel reaction, the stirring speed was increased and uniform particle generation could be promoted.

The supported carrier was dried at 105 ° C to remove water and ground to a particle size of 5 to 10 μm and then calcined at 300 to 500 ° C. for 3 to 6 hours to obtain a reducing agent having a VOCs and odor reducing function.

<Experimental Example 1>

1. Evaluation method of volatile organic compounds (VOCs) emissions by materials

Prepared automobile parts [Rear Shelf] were put into a 1 m ³ chamber and VOCs (Volatile Organic Compound) emissions per automobile parts materials were evaluated. [D49 3027, 3085: 2011, Evaluation of Renault Samsung Automobile VOCs Emissions] Respectively.

2.5 hours after the pretreatment, the air in the chamber was sampled. The flow rate and adsorption amount of the sample are as follows.

0.5 L of Air (Flow rate: 50 mL / min for 10 minutes)

1.5 L of Air (Flow rate: 50 mL / min for 30 minutes)

2. Odor evaluation method by automotive parts [D49 3001_D]

Prepared automobile parts [Rear Shelf] were pretreated at 80 ℃ in accordance with D49 3001_D standard method. The similarity of the 15 kinds of odor characteristics was determined and the average value was calculated.

Evaluation items
(Main Performance Spec) unit Ref Reducing agent applied [5% of total weight] Formaldehyde μg / m ³ 55 13 Acetaldehyde 164 68 Benzene 5 5 Toluene 355 11 Ethylbenzene 22 3 Xlyene 0 4 Styrene 41 2 Odor Rating 3.5 2.1

Table 1 shows the results of VOCs and odor evaluation. It was evaluated that VOCs and odor components were reduced by adding 90% or more of VOCs to Rare Shelf after inserting them into natural composites. In case of sensory rating, it showed excellent level of 2.1 grade level which is less than the global standard value of 2.5.

Evaluation items
(Main Performance Spec) unit Management standard result Flexural strength Mpa 20 or more 39.6 The tensile strength Mpa 15 or more 17.3 Flammability mm / min 120 or more 18 High Temperature / Invasion Appearance condition no problem no problem Peel strength N / cm 5 or more No peeling Impact test Appearance condition no problem no problem

Table 2 shows the results of physical properties after application of the reducing agent prepared according to Example 1 to the automobile parts Rear Shelf. When the 5% by weight of the reducing agent is included in the basic physical properties required as an automobile part, The results are shown.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. It is to be understood that various modifications and changes may be made without departing from the scope of the appended claims.

Claims (12)

Preparing a zeolitic support;
Preparing a composite metal oxide aqueous solution by dissolving at least one metal salt in purified water;
Dissolving an ammonium salt, urea, adipic acid dihydrazide and a surfactant in purified water to prepare a supported solution;
Impregnating the composite metal oxide aqueous solution with a zeolite-based support, and then supporting the zeolite-based support in a supported solution; And
And drying and pulverizing the supported zeolite-based support, followed by calcining, the volatile organic compound material and the odor-inducing substance-reducing agent produced from the natural material. The method according to claim 1,
The step of preparing the zeolite-
Preparing a first solution by dissolving an alkaline agent and an aluminum source in purified water,
Dissolving an alkaline agent, an aluminum source and a silica source in purified water to prepare a second solution,
Reacting the prepared first solution and the second solution at 180 to 240 캜 for 24 to 28 hours, and
And drying the product at 100 to 150 ° C. for 4 to 8 hours. The method for manufacturing a volatile organic compound material and a method for reducing a malodor-inducing substance according to claim 1, The method of claim 2,
The above-
A method for producing a volatile organic compound and a method for reducing a malodor-inducing substance derived from natural materials, wherein the volatile organic compound is derived from sodium hydroxide, potassium hydroxide, lithium hydroxide, and calcium hydroxide. The method of claim 2,
Wherein the aluminum source comprises:
Aluminum oxide, aluminum hydroxide, aluminum alkoxide, aluminum trihydrate, aluminum chloride hexahydrate, aluminum nitrate, aluminum nitrate, nitrate, nonahydrate). The method of claim 1, wherein the volatile organic compound and the odor-inducing substance are derived from natural materials. The method of claim 2,
Wherein the silica source comprises:
Characterized in that it is any one selected from the group consisting of sodium silicate, ethyl silicate, and tetraethyl orthosilicate. The method according to claim 1, wherein the volatile organic compound material and the odor- &Lt; / RTI &gt; The method according to claim 1,
Preferably,
Copper nitrate _{(Cu (NO 3) 2)} , zinc nitrate _{(Zn (NO 3) 2)} , iron nitrate _{(Ⅱ) (Fe (NO 3} ) 2 · 6H 2 O), ferric nitrate (Ⅲ) (Fe (NO ₃ ) ₃ · 6H ₂ O), manganese nitrate _{(Mn (NO 3) 2)} , nickel nitrate _{(Ni (NO 3) 2)} , and silver nitrate (AgNO ₃₎ any one of a nitrate, manganese chloride selected from the group consisting of (MnCl _2), or ferric chloride (FeCl ₂₎ of any one of a chloride, and iron sulfate (FeSO _4), zinc sulfate (ZnSO _4), and cobalt sulfate (CoSO ₄₎ to accomplish the group consisting of any one of a sulfate selected from a binary group , Wherein the volatile organic compound material and the odor-inducing substance are mixed with each other. The method according to claim 1,
The above-
(NH ₄ ) ₂ SO ₄ ), ammonium sulfamate (NH ₄ OSO ₂ NH ₂ ), ammonium nitrate (NH ₄ NO ₃ ), and ammonia water (NH ₄ OH) A volatile organic compound material derived from a natural material, and a method for producing a reducing agent for a malodor causing material. The method according to claim 1,
The surfactant,
Wherein the volatile organic compound derived from a natural material and the odor inducing agent are any one selected from the group consisting of a nonionic surfactant, a cationic surfactant and an ionic surfactant. A method for manufacturing a substance reducing agent. The method according to claim 1,
Drying, pulverizing and calcining the supported zeolite odor reducing support,
Characterized in that the supported zeolite odor-reducing support is dried at 90 to 110 캜, ground to an average particle size of 5 to 10 탆, and then calcined at 300 to 500 캜 for 3 to 6 hours. VOLATILE ORGANIC COMPOUND MATERIAL AND METHOD FOR MANUFACTURING SOME REDUCING AGENT. A volatile organic compound material and a malodor causing material-reducing agent derived from a natural material, which are produced according to any one of claims 1 to 9. An adsorbent material comprising a reducing agent according to claim 10. The method of claim 11,
The adsorbent material,
And 3 to 10 parts by weight of a reducing agent for 100 parts by weight of the adsorbent material.

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