KR100519461B1 - Natural zeolite-supported catalyst, method of manufacturing the same, and method of removal of n2o using the same - Google Patents

Abstract

Disclosed are a catalyst, a method for preparing the same, and a method for removing nitrogen oxides, such as nitrous oxide, which are excellent in price and at the same time have an excellent effect of removing nitrogen oxides such as nitrous oxide. To this end, there is provided a natural zeolite carrier catalyst having a natural zeolite carrier and an active material which is Fe, Co, or Cu. In addition, the natural zeolite acid treatment, and then the acid-treated natural zeolite primary ion-exchange using an aqueous solution of ammonium compound, and then a method for producing a natural zeolite carrier catalyst supporting the active material in the primary ion-exchanged natural zeolite To provide. In addition, the present invention provides a method for removing a N 2 O or the like by using a natural zeolite carrier catalyst or a direct decomposition or reducing agent. By using natural zeolite as a support instead of synthetic zeolite, a low-cost catalyst can be produced, and process investment and maintenance costs can be reduced, thereby enabling economic removal of nitrous oxide.

Description

NATURAL ZEOLITE-SUPPORTED CATALYST, METHOD OF MANUFACTURING THE SAME, AND METHOD OF REMOVAL OF N2O USING THE SAME}

The present invention relates to a catalyst and a method for removing nitrous oxide using the same, and more particularly, to a catalyst having excellent nitrogen oxide removal effect using a natural zeolite as a support, a method for preparing the same, and a method for removing nitrous oxide using the same. will be.

Nitrous oxide (N2O) is a colorless and transparent gas produced by pyrolysis of ammonium nitrate and is included in the exhaust gas along with general nitrogen oxides (NOx). Nitrous oxide causes cramps in facial muscles, and research has been widely conducted to remove it from the exhaust gas using a catalyst as an anesthetic gas.

Synthetic zeolites are mainly used as catalyst carriers in catalyst systems for removing nitrous oxide. Synthetic zeolites may include the most widely used ZSM-5 catalysts, MFI (following the IUPAC committee's zeolite nomenclature, the same below), MOR, and the like, and these synthetic zeolite catalysts may be prepared by direct physical property manufacturing. do. On the other hand, the active material components supported on the zeolite support described above may be exemplified iron, cobalt, copper, etc., by using such a catalyst system to directly decompose nitrous oxide or selectively remove nitrous oxide using a reducing agent.

Specifically, Korean Patent Laid-Open Publication No. 10-1993-0009637 includes a metal ion selected from copper, cobalt, rhodium, iridium, ruthenium, and palladium, and a catalyst using a synthetic zeolite such as Beta, MOR, MFI, MEL, and FER as a catalyst carrier. A catalytic cracking method of N 2 O used is disclosed.

In addition, Korean Patent Publication No. 10-2002-0081309 discloses a technique for decomposing N 2 O using a catalyst composed of a cobalt oxide compound (0.1-50%) and a magnesium compound (50-99.9%).

Although all of the above-described inventions provide a technique for removing nitrous oxide, all have a fundamental catalytic difference from natural zeolites by using synthetic zeolites. In addition, in the case of a catalyst supporting the active material and a catalyst including the active material, most of the zeolite components corresponding to the support will determine the price. The synthetic zeolite described above has a price in terms of process investment and maintenance. The cause of the rise is large.

In view of the problems of the synthetic zeolite, a technique for removing harmful gases using natural zeolite has been developed. That is, Korean Patent Publication No. 10-2002-0051049 discloses a technique for adsorbing and removing carbon monoxide using a catalyst using natural zeolite. However, in the case of the present invention, since the purpose of the removal of carbon monoxide, not nitrous oxide, is different, its function is different, and since only the first pretreatment is used without an active substance, only the adsorbent is used, so that the efficiency is inevitably deteriorated. have.

In addition, the type of catalyst to be prepared may be utilized by directly forming a catalyst coated or prepared on a substrate having a variety of shapes, the above-described invention is a specific technology for the shape catalyst manufacturing field for removing N 2 O It does not present a composition.

On the other hand, Korean Patent Laid-Open Publication No. 10-2002-0081255 provides a two-stage catalytic reactor using an iron-supported catalyst in synthetic zeolites (MFI, BEA, FER, MOR, MEL) and using ammonia as a reducing agent. This makes it possible to simultaneously remove NOx and N2O. That is, the patent consists of two catalyst layers (dual catalytic reactors) that can be selectively removed from each of these pollutants in order to effectively reduce N2O and NOx at the same time, and N2O and NOx are each injected with different species of reducing agent having high selectivity. This is disadvantageous in terms of price competitiveness than using a single catalyst layer.

Therefore, there is a need for a technology development for a catalyst that can effectively remove nitrous oxide as well as other nitrogen oxides at the same time by using natural zeolite with excellent price competitiveness as a support.

Accordingly, it is a first object of the present invention to provide a catalyst having excellent cost competitiveness and excellent nitrogen oxide removal efficiency such as nitrous oxide.

It is a second object of the present invention to provide a method for preparing the catalyst.

A third object of the present invention is to provide a method for removing nitrogen oxides such as nitrous oxide using the catalyst.

In order to achieve the first object of the present invention described above, an embodiment of the present invention is supported on natural zeolite and natural zeolite, and includes at least one active material selected from the group consisting of Fe, Co, and Cu It provides a natural zeolite carrier catalyst.

In order to achieve the above-described second object of the present invention, according to one embodiment of the method for producing a natural zeolite carrier catalyst of the present invention, the first mixture containing the natural zeolite and an acidic solution is heated to acid Treatment, followed by heating a second mixture comprising an acid treated aqueous solution of natural zeolite and ammonium compound to primary ion exchange the acid treated natural zeolite followed by a first aqueous solution of ionized natural zeolite and active material precursor The third mixture is heated to secondary ion exchange to produce a natural zeolite carrier catalyst.

Here, the active material precursor is a compound of a metal ion selected from the group consisting of Fe ions, Co ions, and Cu ions and an anion selected from the group consisting of NO3-, CO3-, Cl-, and SO42-.

In order to achieve the above-mentioned third object of the present invention, according to one embodiment of the method for removing nitrous oxide and the like of the present invention, first, a natural zeolite carrier catalyst comprising a natural zeolite and an active substance supported on the natural zeolite After the preparation, the prepared natural zeolite carrier catalyst is reacted with N 2 O to remove N 2 O and the like.

In order to achieve the above-mentioned third object of the present invention, according to another embodiment of the method for removing nitrous oxide and the like of the present invention, first, a natural zeolite carrier catalyst comprising a natural zeolite and an active substance supported on the natural zeolite After the preparation, the prepared natural zeolite carrier catalyst is reacted with N 2 O and a reducing agent to remove N 2 O and the like.

 According to the present invention, by using a natural zeolite as a support instead of a synthetic zeolite, it is possible to manufacture a low-cost catalyst and to reduce the process investment and maintenance costs, thereby enabling economic removal of nitrous oxide. And because the process according to the invention has a wide operating temperature (operating temperature) is applicable to the post-treatment technology of various processes, such as fluidized bed incineration plant, nitric acid manufacturing process, various industrial combustion equipment.

In addition, by using a reducing agent and a denitration catalyst suitable for the catalyst according to the present invention, it is possible to remove not only nitrous oxide but also all types of nitrogen oxides in a continuous process at the same time.

Hereinafter, the present invention will be described in more detail.

First, the present invention provides one embodiment of a catalyst having a natural zeolite as a support.

The natural zeolite carrier catalyst comprises a natural zeolite. As the natural zeolite, an HEU-based catalyst or the like may be used, and is prepared through acid treatment and primary ion exchange described later.

For example, an acid treatment of heating at 90 to 97 ° C. for 7 hours using an acidic solution such as NH 4 Cl or HCl is repeated four times, and washed five times or more with distilled water to have a surface pH of the solid sample in the range of 7. When the washed sample is dried at 110 ° C. for 24 hours and calcined at 500 ° C. for 4 hours, the natural zeolite increases its specific surface area to 220 m 2 / g, 0.4% by weight of sodium, and 0.02 weight % Potassium and 0.2% calcium are reduced.

In addition, the natural zeolite carrier catalyst of the present embodiment includes an active material supported on the natural zeolite. The active material is Fe, Co, Cu, or a mixture thereof, which is prepared by heating a first ion-exchanged natural zeolite carrier catalyst on a precursor aqueous solution of the active material and performing secondary ion exchange.

Here, the prepared natural zeolite carrier catalyst contains about 95 to 99.99% by weight of the natural zeolite and about 0.001 to 5% by weight of the active material. If the amount of the active substance is less than about 0.001% by weight, the amount of the active substance is insignificant, which makes it difficult to effectively remove nitrous oxide, etc. There is a difficult problem.

In the present invention, it is possible to economically remove nitrous oxide and the like by using natural zeolite whose price is only about 1/100 of that of synthetic zeolite.

1 is a flow chart illustrating an embodiment of a method for preparing a natural zeolite carrier catalyst according to the present invention. Referring to Figure 1 and describes an embodiment of the method for producing a natural zeolite carrier catalyst of the present invention, first, the acid-treated natural zeolite (S10), the acid-treated natural zeolite using an aqueous solution of ammonium compound 1 After primary ion exchange (S20), the primary ion-exchanged natural zeolite is subjected to secondary ion exchange using an active material precursor aqueous solution (S30).

First, the natural zeolite is acid treated (S10).

As said natural zeolite, HEU type natural zeolite can be used, for example. Natural zeolites are only about 1/100 the price of synthetic zeolites, which is an economic advantage.

The acid treatment is carried out by heating the first mixture of the natural zeolite and an acid solution such as NH 4 Cl or HCl at 90 to 97 ° C. for 5 to 9 hours. If the temperature is less than 90 ℃ or the reaction time is less than 5 hours, there is a problem that the catalyst is not sufficiently supported, if it exceeds 97 ℃ or more than 9 hours it is economically undesirable and uniform on the zeolite by acid treatment for a long time There is a fear that the pores distributed in a good manner will be destroyed.

It is most preferable to repeat the process of acid treatment by heating the first mixture for 7 hours at a temperature range of 90 to 97 ℃.

In addition, the post-treatment process may be repeated after the acid treatment, and the post-treatment process described below may be performed after each step of the present embodiment. The post treatment is performed by washing the acid treated natural zeolite with distilled water, drying the washed natural zeolite, and calcining the dried natural zeolite. For example, by washing five times or more with distilled water to maintain the surface pH of the solid sample in the range of 7, the washed sample is dried for 24 hours at 110 ℃ and then calcined at 500 ℃ for 4 hours A catalyst support sample is prepared.

 After this acid treatment, the natural zeolite is reduced in alkali metals such as Na, K, Ca and the specific surface area is increased. In other words, impurities are removed and the specific surface area for nitrous oxide removal is greatly increased, so that effective nitrous oxide removal is possible.

Subsequently, the acid treated natural zeolite is first ion exchanged using an aqueous ammonium compound solution (S20).

Here, as the aqueous solution of ammonium compound, NH 4 NO 3, NH 4 Cl or a mixture thereof can be used, and the conditions of the primary ion exchange reaction are similar to the acid treatment conditions. That is, the second mixture of the acid-treated natural zeolite and the aqueous ammonium compound solution is heated at 90 to 97 ° C. for 5 to 9 hours. In addition, after the first ion exchange, as in the acid treatment process, the first ion-exchanged natural zeolite is washed with distilled water, the washed natural zeolite is dried, and the post-treatment process of firing the dried natural zeolite. You can add For example, by washing five times or more with distilled water to maintain the surface pH of the solid sample in the range of 7, the washed sample is dried for 24 hours at 110 ℃ and then calcined at 500 ℃ for 4 hours do.

Since the active materials (Fe, Co, Cu) exist in the form of bivalent or more ions in solution, the zeolite (zero-valent) calcined and manufactured on the surface of the supported zeolite by primary ion exchange is preferentially monovalent (here, ammonium). (NH4 +) to make secondary ion exchange more efficient.

Finally, the primary ion-exchanged natural zeolite is subjected to secondary ion exchange using an active material precursor aqueous solution (S30).

As the active material precursor, a compound of a metal ion selected from the group consisting of Fe ions, Co ions, and Cu ions and an anion selected from the group consisting of NO3-, CO3-, Cl-, and SO42- is used. For example, Fe (NO 3) 3, Co (NO 3) 2, Cu (NO 3) 2, or the like can be used.

The secondary ion exchange is also carried out by heating the third mixture containing the primary ion-exchanged natural zeolite and the active material precursor aqueous solution at 90 to 97 ℃ for 5 to 9 hours. In addition, after the secondary ion exchange, the secondary ion exchanged natural zeolite is washed with distilled water, the dried natural zeolite is dried, and the dried natural zeolite is dried, as in the post treatment of the primary ion exchanged natural zeolite. It may also be fired.

After the secondary ion exchange, the amount of the active substance supported on the prepared catalyst is about 0.001 to 5% by weight. The natural zeolite carrier catalyst prepared by the above method is very inexpensive in terms of cost because it uses a natural zeolite rather than a synthetic zeolite as a carrier, and can remove not only nitrous oxide but also other nitrogen oxides simultaneously with a single catalyst layer.

In another aspect, the present invention provides embodiments of a method for removing nitrous oxide and the like using the prepared natural zeolite carrier catalyst.

Figure 2 is a flow chart illustrating an embodiment of a method for removing nitrous oxide and the like using a natural zeolite carrier catalyst according to the present invention. Referring to FIG. 2, a natural zeolite carrier catalyst is prepared and prepared by the method disclosed in FIG. 1 (S110), and N 2 O is removed using the prepared natural zeolite carrier catalyst (S120).

First, a natural zeolite carrier catalyst comprising a natural zeolite and an active material supported on the natural zeolite is prepared (S110). The natural zeolite carrier catalyst is prepared by the method disclosed in FIG.

Subsequently, N 2 O is removed by reacting the prepared natural zeolite carrier catalyst with N 2 O (S120).

For example, specific reaction conditions may be performed at 500 to 650 ° C. in an oxygen atmosphere. This is a direct decomposition method in which no reducing agent is injected. If it is less than 500 ° C., the removal of nitrous oxide is insufficient, and if it exceeds 650 ° C., a large amount of energy is required for high temperature, which is not economically desirable.

At this time, looking at the reactor for the removal of nitrous oxide using a direct decomposition or reducing agent without using a reducing agent as follows.

2N2O → 2N2 + O2 [Scheme 1]

4N2O + CH4 → 4N2 + CO2 + 2H2O [Scheme 2]

2N2O + CH4 + O2 → 2N2 + CO2 + 2H2O [Scheme 3]

3N2O + 2NH3 → 4N2 + 3H2O [Scheme 4]

N2O + 2NH3 + O2 → 2N2 + 3H2O [Scheme 5]

The reaction schemes 1 to 5 are reactions required for N 2 O removal, but since the operating temperature of the catalyst is mostly operated in a temperature range of 400 to 600 ° C., a reaction in which the reducing agent is oxidized in a reaction including reducing agents (CH 4 and NH 3) is performed. Is also observed at the same time. When NH 3 is used as a reducing agent, a reaction of removing N 2 O and a competition reaction may occur in an oxygen atmosphere as shown in Schemes 6 to 8 below.

4NH3 + 3O2 → 2N2 + 6H2O [Scheme 6]

4NH3 + 4O2 → 2N2O + 6H2O [Scheme 7]

4NH3 + 5O2 → 4NO + 6H2O [Scheme 8]

CH4 + 2O2 → CO2 + 2H2O [Scheme 9]

Schemes 6 to 9 are reactions that should be suppressed as much as possible. In Schemes 6 and 9, the peak of N 2 O removal activity is observed due to the oxidation reaction of the reducing agent and may decrease again. In addition, since Scheme 7, 8 generates N 2 O and NO, it is necessary to select a catalyst that does not proceed as a path of the reaction.

The natural zeolite catalyst prepared in the present invention is produced by a direct decomposition reaction (Scheme 1) and a reaction using methane as a reducing agent (Scheme 3) under an excess oxygen atmosphere as a change experiment of injection concentration and a transient behavior test. You can check it. Competitive reactions and side reactions are not identified by investigating the concentration change of gas produced by gradually increasing the limiting reactant concentration in the reaction mechanism under fixed reaction temperature.

3 is a flow chart for explaining another embodiment of a method for removing nitrous oxide and the like using the natural zeolite carrier catalyst according to the present invention. Referring to FIG. 3, a natural zeolite carrier catalyst is prepared and prepared by the method disclosed in FIG. 1 (S210), and N 2 O is removed using the prepared natural zeolite carrier catalyst and a reducing agent (S220).

First, a natural zeolite carrier catalyst comprising a natural zeolite and an active material supported on the natural zeolite is prepared (S210). The natural zeolite carrier catalyst is prepared by the method disclosed in FIG.

Subsequently, N 2 O is removed using the prepared natural zeolite carrier catalyst and a reducing agent (S220).

As the reducing agent, methane, propane, propylene, ammonia, urea, or a mixture thereof may be used. And the removal of the nitrous oxide is carried out at 400 to 550 ℃ because it is possible to effectively remove the nitrous oxide even by controlling the process temperature lower than the direct decomposition by using a reducing agent. For example, while using nitrous oxide at a space velocity of 5,000 to 30,000 / hr, He is used as a mixed gas at a reaction temperature of 300 to 600 ° C., an injection ratio ([CH 4] / [N 2 O]) of 1 to 2, and oxygen of 2%. Nitrous oxide is removed. When the other conditions are the same, the iron-exchanged catalyst shows the best activity as a result of reacting methane (CH4), which is a reducing agent, at the same concentration as N2O.

The present invention will be described in more detail with reference to the following examples. However, an Example is for illustrating this invention and is not limited only to these.

EXAMPLE

Example 1 Preparation of Natural Zeolite Support Catalyst

(Acid treatment)

Natural zeolites (NZ) contain a lot of impurities in order to be used directly as a catalyst raw material in a natural state, and have a very low specific surface area and acid point distribution required as a catalyst. Therefore, it was used after treatment in acid solution in order to have such catalytic properties before use. In this example, 800 ml of an aqueous solution of NH 4 Cl (or HCl) at a concentration of 1N was prepared and mixed with 300 g of natural zeolite, and subjected to acid treatment four times or more at 90 to 97 ° C. for 7 hours. In particular, in each treatment step was washed five times or more with secondary distilled water to maintain the surface pH of the solid sample in the range of 7. The washed sample was dried for 24 hours at 110 ° C. and calcined at 500 ° C. for 4 hours to prepare a catalyst support sample (HNZ). As mentioned above, the primary zeolite treated with acid was significantly reduced in alkali element components in the raw material sample. As a result of elemental analysis of the catalyst sample before and after treatment, Na was 2.1% to 0.4%, and K was 2.3%. At 0.02%, Ca decreased from 0.4% to 0.2%, respectively. The specific surface area also increased from 45m2 / g to 220m2 / g.

(Primary ion exchange)

In order to effectively support the catalytically active materials iron, cobalt, copper and the like on the natural zeolite thus prepared, first, an aqueous solution of NH 4 NO 3 or NH 4 Cl 0.1N was prepared, and primary ion exchange was performed. The preparation conditions were carried out almost similarly to the acid treatment conditions, and were ion exchanged at 95 ° C. for 7 hours and washed five times with distilled water after the first ion exchange. The washed samples were dried at 110 ° for 24 hours.

(Secondary ion exchange)

In order to support the active materials iron, cobalt, and copper on the primary ion-exchanged natural zeolite, 0.1 N of the active material precursors of Fe (NO 3) 3, Co (NO 3) 2 and Cu (NO 3) 2 were prepared. Primary ion exchange was performed. The slurry mixed with 300 g natural zeolite acid-treated in 500 ml aqueous solution was subjected to secondary ion exchange at 95 ° C. for 7 hours. Finally, the final N 2 O removal catalyst was prepared by drying at 110 ° C. for 24 hours and firing at 500 ° C. for 4 hours. The catalysts in which the active material was ion-exchanged with iron, cobalt, and copper were called Fe / HNZ, Co / HNZ, and Cu / HNZ, respectively. The amount of active material supported under the same conditions was Fe (4.5%). , Co (0.3%) and Cu (2.7%) were observed, respectively.

Example 2 Removal of Nitrous Oxide

Table 1 below shows the N 2 O removal performance of the catalyst according to the reaction temperature by injecting methane, which is a space velocity of 15,000 / hr, and reducing agent, at the same concentration as N 2 O, for the catalysts prepared in Example 1. The prepared catalysts can be used according to the reaction temperature, and it was observed that the iron-ionized natural zeolite catalyst has a relatively wide operating temperature.

Reaction temperature (℃) % N2O removal conversion Fe / HNZ Co / HNZ Cu / HNZ 300 7.4 3.7 3.4 350 39.6 29.6 4.97 400 81.3 63.3 13.1 450 97.8 90.9 36.7 500 100 100 69.5 550 100 100 97.6

Example 3 Direct Degradation Activity Comparison

Table 2 below shows the N 2 O removal reaction for the catalysts prepared in Example 1 without injection of a reducing agent. Specifically, the observation was to compare the activity in the mixed gas conditions containing space velocity 15,000 / hr, 2% oxygen. The reaction showed a lower activity of less than 50% up to 450 ° C., but the cobalt ion-exchanged catalyst (Co / HNZ) showed a 100% removal activity at temperatures above 600 ° C. In the direct decomposition reaction, cobalt showed high activity irrespective of the amount of active substance supported, so it could be applied to the process without reducing agent.

Reaction temperature (℃) N2O direct decomposition conversion rate (%) Fe / HNZ Co / HNZ Cu / HNZ 300 - - 0.2 350 3.1 3.0 0.7 400 9.0 12.9 2.4 450 12.2 38.1 5.3 500 18.2 73.4 15.9 550 38.2 95.5 55.0 600 72.1 100 97.2 650 96.3 100 100

 Example 4 Activity According to Fe / HNZ Catalytic Reducing Agent

Table 3 compares the N 2 O removal activity according to the reaction temperature at a space velocity of 15,000 / hr for reducing agents such as methane, propane, and ammonia for the Fe / HNZ catalyst. In the case of the reducing agent, methane showed the best N2O removal activity, and ammonia showed the lowest activity in the N2O reduction reaction, except that α = [reducing agent injection concentration] / [N2O concentration].

Reaction temperature (℃) % N2O removal conversion CH4 (α = 2) CH4 (α = 1) C3H8 (α = 1) NH3 (α = 1) 300 11.7 7.4 9.7 0.0 350 44.7 39.6 32.5 11.1 400 88.7 81.3 78.4 29.2 450 100 97.8 100 42.3 500 67.8 550 98.5

According to the present invention, by using a natural zeolite as a support instead of a synthetic zeolite, it is possible to manufacture a low-cost catalyst, and to reduce the process investment and maintenance costs, thereby enabling economic removal of nitrous oxide.

And because the process according to the invention has a wide operating temperature (operating temperature) is applicable to the post-treatment technology of various processes, such as fluidized bed incineration plant, nitric acid manufacturing process, various industrial combustion equipment.

In addition, by using a reducing agent and a denitration catalyst suitable for the catalyst according to the present invention, it is possible to remove not only nitrous oxide but also all types of nitrogen oxides in a continuous process at the same time.

Although described above with reference to a preferred embodiment of the present invention, those skilled in the art will be variously modified and changed within the scope of the invention without departing from the spirit and scope of the invention described in the claims below I can understand that you can.

1 is a flow chart illustrating an embodiment of a method for preparing a natural zeolite carrier catalyst according to the present invention.

Figure 2 is a flow chart illustrating an embodiment of a method for removing nitrous oxide and the like using a natural zeolite carrier catalyst according to the present invention.

3 is a flow chart for explaining another embodiment of a method for removing nitrous oxide and the like using the natural zeolite carrier catalyst according to the present invention.

Claims (7)

Natural zeolite containing 0.01 wt% to 0.4 wt% of an alkali metal; And A natural zeolite carrier catalyst supported on the natural zeolite and comprising at least one active material selected from the group consisting of Fe, Co, and Cu. The natural zeolite carrier catalyst according to claim 1, wherein the alkali metal is any one selected from the group consisting of sodium, potassium and calcium. According to claim 1, 95 to 99.99% by weight of the natural zeolite; And Natural zeolite carrier catalyst comprising 0.01 to 5% by weight of the active material. Acid treating the natural zeolite by heating the first mixture including the natural zeolite and the acidic solution at 90-97 ° C. for 5-9 hours; Primary ion exchange of the acid-treated natural zeolite by heating a second mixture including the acid-treated natural zeolite and an aqueous ammonium compound solution at 90-97 ° C. for 5-9 hours; And  Activity of the primary ion-exchanged natural zeolite and a compound of a metal ion selected from the group consisting of Fe, Co, and Cu ions and an anion selected from the group consisting of NO3-, CO3-, Cl-, and SO42- A method of producing a natural zeolite carrier catalyst comprising heating a third mixture comprising an aqueous solution of a material precursor for 2-9 hours at 90-97 ° C. for 5-9 hours. a) natural zeolite containing 0.01% to 0.4% by weight of an alkali metal; And Preparing a natural zeolite carrier catalyst supported on the natural zeolite and including at least one active material selected from the group consisting of Fe, Co, and Cu; b) removing the nitrous oxide comprising the step of removing the N2O by reacting the prepared natural zeolite carrier catalyst and N2O at 500 ~ 650 ℃. a) natural zeolite containing 0.01% to 0.4% by weight of an alkali metal; And Preparing a natural zeolite carrier catalyst supported on the natural zeolite and including at least one active material selected from the group consisting of Fe, Co, and Cu; b) a method of removing nitrous oxide comprising the step of removing the N 2 O by reacting the prepared mixture containing the natural zeolite carrier catalyst, a reducing agent and N 2 O at 400 ~ 550 ℃. 7. The method for removing nitrous oxide according to claim 6, wherein the reducing agent is at least one selected from the group consisting of methane, propane, propylene, ammonia, and urea.