KR101276103B1 - low temperature activity catalysts used in filter for exhaust gas of ship, preparing method thereof and filter for exhaust gas of ship - Google Patents

Abstract

A low temperature active catalyst for marine exhaust gas filters is disclosed. Low temperature active catalyst for ship exhaust gas filter according to an embodiment of the present invention, in the catalyst for removing nitrogen oxides contained in the exhaust gas, zeolite carrier FeZSM5, 1 to 3% by weight of Cu based on the FeZSM5, Aluminasol 5-20 Percent by weight;

Description

Low temperature activity catalysts used in filter for exhaust gas of ship, preparing method etc and filter for exhaust gas of ship}

The present invention relates to a low temperature active catalyst that can be used in a ship exhaust gas filter, a manufacturing method thereof, and a ship exhaust gas filter to which the same is applied.

Exhaust gases of automobiles and ships equipped with internal combustion engines include nitrogen oxides (NOx) such as NO, NO ₂ and N ₂ O, which cause photochemical smog and acid rain, and are generally exhausted to reduce nitrogen oxide emissions. Exhaust gas purification filters which inject a reducing agent such as ammonia or urea into gas and convert them into harmless N _{2 and} H ₂ O through a catalytic reaction are used.

The law on nitrogen oxide emissions is strictly applied.In particular, the International Maritime Organization (IMO) has reduced the ship engine nitrogen oxide emissions from 14.4g to 3.4g per ㎾h since 2016 to prevent marine pollution. The trend is getting stronger.

Generally, the exhaust gas temperature of an automobile engine is 250-450 degreeC, and the exhaust gas temperature of a ship engine is 150-250 degreeC, and the exhaust gas purification filter used for ship engines is compared with the exhaust gas purification filter applied to automobiles. It is required to make the activity smooth even at low temperatures.

Nitrogen oxide reduction technology conventionally applied to ships and plants includes an extrusion catalyst filter made by extruding a vanadia (V ₂ O ₅ ) -based catalyst material, but the cell density is too low Is very large, and at high temperatures, the activity of the catalyst is drastically lowered, and its use is regulated due to the toxicity of vanadium.

[Table 1] below summarizes the results of experiments on nitrogen oxide reduction efficiency of one embodiment of a conventional extrusion catalyst filter based on Vanadia (V ₂ O ₅ ) and PILC (Pillared Interlayer Clay) in the temperature range of 150 ~ 200 ° C. It is.

Experimental conditions are N ₂ balance, NO 500 ppm, NH ₃ 500 ppm, O ₂ 11%, Water 10%, SV (Space Velocity) 40000 h ⁻¹ .

Temp. [℃]

150
155
160
165
170
175
180
185
190
195
200
DeNOx [%]

35
38
45
49
55
60
65
68
70
72
75

As can be seen from [Table 1], in the past, the nitrogen oxide reduction efficiency of more than 80% could not be expected below 200 ° C, and it could meet the trend of heightened awareness and awareness of environmental pollution and marine pollution prevention. There is an urgent need for the development of low temperature active catalyst technology.

Embodiments of the present invention can implement a nitrogen oxide reduction efficiency of more than 90% in the 190 ~ 200 ℃ temperature range, to provide a low temperature active catalyst suitable for application to a ship exhaust gas filter, a manufacturing method and a marine exhaust gas filter using the same do.

The present invention for achieving the object as described above, in the catalyst for removing nitrogen oxides contained in the exhaust gas, zeolite carrier FeZSM5, 1 to 3% by weight of Cu, 5 to 20% by weight of Aluminasol; The low temperature active catalyst for ship exhaust gas filter comprised is a technical subject matter.

Here, Mn 1 to 5% by weight relative to the FeZSM5; may be configured to further include.

In addition, the FeZSM5 Mn 1 ~ 5% by weight, Ca 1 ~ 5% by weight; may be configured to further include.

In addition, the Aluminasol may be composed of a sol having a needle-like structure of Alumina monocomponent.

In addition, the present invention, a method for producing a catalyst for removing nitrogen oxide contained in the exhaust gas, the first step of stirring DI water and Cu precursor; A second step of stirring the stirred material of the first step and FeZSM5, wherein the Cu is 1 to 3% by weight relative to the FeZSM5; And a third step of stirring the aluminasol and the aluminasol of the second step, wherein the aluminasol is stirred at 5 to 20% by weight with respect to the FeZSM5. It is a technical point.

Here, it is made in a temperature environment of 50 ~ 80 ℃, FeZSM5: DI water may have a weight ratio of 3 to 5: 6 to 8.

In addition, the first step may be performed for 30 min, the second step may be performed for 1 to 3 hrs, and the third step may be performed for 1 to 2 hrs.

In addition, the first step, 1 to 5% by weight of the Mn precursor with respect to FeZSM5 may be further stirred.

In addition, the first step, 1 to 5% by weight of Mn precursor, Ca 1 to 5% by weight relative to the FeZSM5 may be further stirred.

In addition, the first step, the first-first step of stirring the DI water, Cu precursor, Mn precursor; It may be configured to include; and 1-2 steps of stirring the DI water, Mn precursor, Ca precursor.

In addition, in the second step, the stirred material of the first-first step, the stirred material of the first-second step, and FeZSM5 may be stirred.

In addition, the first-first step and the first-second step may be 30 to 50 min, the second step may be 3 to 5 hrs, and the third step may be performed for 1 to 2 hrs.

The present invention also provides a low temperature active catalyst for ship exhaust gas filter according to claim 1 or a low temperature active catalyst for ship exhaust gas filter according to claim 5 on a metal substrate 10 or a ceramic substrate. Another technical subject is a marine exhaust gas filter formed by coating a catalyst.

Here, the metal substrate 10 may be formed on the surface of the concave-convex to enlarge the coating area per unit area of the catalyst than the flat plate.

In addition, the irregularities of the metal substrate 10 may have a height, a depth, or a width of about 0.2 μm or more and about 1.5 μm or less, and may be uniformly formed throughout the metal substrate 10.

In addition, the unevenness of the metal substrate 10 is acute angle due to the decrease in surface tension of the catalyst having a viscosity that the edge portion is an obtuse angle in the state attached to the flat plate, attached to the metal substrate 10 It can be formed in a size and density to achieve.

According to the low temperature active catalyst according to the embodiments of the present invention, it is possible to stably implement a high nitrogen oxide reduction efficiency of 90% or more in the low temperature region of 190 ~ 200 ℃ or less, in particular, the exhaust gas temperature range of 150 ~ 250 ℃ When the branch is applied for the exhaust gas treatment of the ship, it is possible to realize a significantly superior purification performance compared to the existing vessel exhaust gas treatment technology.

In addition, it is possible to realize a significantly superior adhesion and binding force in water, compared to the existing extrusion catalyst filter, to prevent the reduction of nitrogen oxide purification performance as the catalyst is removed from the substrate as the use time elapses, the catalyst site is reduced The longer lifespan can be achieved.

In addition, by providing fine concavities and convexities on the surface of the metal substrate, in removing the nitrogen oxides emitted from the ship engine, the volume of the filter is minimized to increase the space utilization, and to improve the performance of reducing the nitrogen oxides by improving the catalyst coating property and the surface area. It is to let.

1 is a conceptual diagram illustrating a state in which a low temperature active catalyst for a ship exhaust gas filter according to an embodiment of the present invention is coated on a metal substrate having irregularities
Figure 2-conceptual diagram showing an example of forming the irregularities on the metal substrate with a roller
3-A conceptual diagram showing an example of forming irregularities on the roller surface by shot blasting

Hereinafter, in the description of the low temperature active catalyst for ship exhaust gas filter according to the present invention in detail, the first, second, and third examples will be described, the method for producing a low temperature active catalyst for ship exhaust gas filter according to the present invention. In the following description, the first, second and third embodiments corresponding to the method for preparing each of the first, second and third embodiments of the low temperature active catalyst will be described.

In addition, the ship exhaust gas filter according to the present invention is the first, third and fifth embodiments to which the first, second and third embodiments of the low temperature active catalyst for the ship exhaust gas filter are applied to a metal substrate, respectively, and the vessel to a ceramic substrate. The second, fourth and sixth embodiments to which the first, second and third embodiments of the low temperature active catalyst for the exhaust gas filter are applied will be described.

Applicant's research and experiment results show that ZSM5, Nitrate or Acetate-based cocatalysts (e.g. Cu, Mn, Ca, etc.) among various zeolite carriers are preferably applied, and the metal components (the cocatalysts) are supported. Before the above, it is preferable to use Fe-ZSM5, in which Fe is substituted, using Fe in the zeolite catalyst ZSM5 by ion exchange method in advance.

Accordingly, embodiments of the present invention, including the first, second and third embodiments of the low temperature active catalyst for marine exhaust gas filters, are ion exchanged zeolite carriers Fe-ZSM5, cocatalysts Cu, Mn, Ca Include as a component.

First, the first embodiment of the low temperature active catalyst for ship exhaust gas filter, the first embodiment of the method for producing the low temperature active catalyst for ship exhaust gas filter, and the first and second embodiments of the ship exhaust gas filter will be described. Shall be.

The first embodiment of the low temperature active catalyst for ship exhaust gas filter, for removing the nitrogen oxide contained in the exhaust gas, 1 to 3% by weight of Cu and 5 to 10% by weight of Aluminasol based on the zeolite carrier FeZSM5, FeZSM5 It is configured to include.

In preparing the first embodiment of the low temperature active catalyst, the first step of stirring DI water and Cu precursor, the second step of stirring the stirred material and FeZSM5 of the first step, and the stirring of the second step The third step of stirring water and Aluminasol is carried out sequentially.

The first embodiment of the low temperature active catalyst production method is made in the temperature environment of the 50 ~ 80 ℃, the Cu in the first step, 1 ~ to the FeZSM5 to be stirred in the second step Stirred at 3% by weight, in the third step, the Aluminasol is stirred at 5 to 10% by weight relative to the FeZSM5 in the form of a sol having a needle-like structure of Alumina monocomponent.

The FeZSM5 and DI (DeIonize) water (pure water without ions) have a weight ratio of 3 to 5: 6 to 8 (eg, FeZSM5 30 to 50 g, DI water 60 to 80 ml), and the first In the step 30 min, in the second step 1 to 3 hrs, in the third step is continuously stirred for 1 to 2 hrs.

The first embodiment of the marine exhaust gas filter, as shown in Figure 1, the first embodiment of the low temperature active catalyst for the marine exhaust gas filter on the surface of the metal substrate 10, or the marine exhaust gas filter It has a configuration in which the catalyst prepared by the first embodiment of the method for preparing a low temperature active catalyst is coated.

In the embodiment shown in Figure 1, the surface of the metal substrate 10 is formed with irregularities for expanding the coating area per unit area of the catalyst than the flat plate.

When the catalyst 20 is coated on the metal substrate 10 having the unevenness, the edge portion of the catalyst 20 to be adhered to the metal substrate 10 is attached to the flat metal base material. , With a smaller angle, even contact of the same mass over a larger area.

That is, when the material 20 is coated on the surface of the metal substrate 10 on which the unevenness is formed, the surface tension of the catalyst 20 in the liquid phase is reduced by the unevenness, and thus, per unit mass of the catalyst 20. The coating is performed in a state where the attachment area is larger than that of the flat plate.

In forming the unevenness on the plate, it is formed to a size and density that can reduce the surface tension of the catalyst 20 in the liquid phase attached to the uneven surface of the metal substrate 10, into the liquid catalyst 20 As the surface area of the metal substrate 10 to be introduced is maximized, the surface tension of the catalyst 20 may be effectively attenuated.

The deeper and deeper the irregularities, the more the surface area can be enlarged. However, since the metal substrate is generally manufactured using a metal sheet having a thickness of 100 μm or less, the strength is maintained in consideration of the air pressure according to the progress of exhaust gas. In order to achieve this, it is preferable to form irregularities with a fine size having a height, a depth or a width of 0.2 µm or more and 1.5 µm or less.

The size and density of the unevenness vary depending on the material of the metal substrate 10, the volume of the metal filter, the exhaust gas reduction efficiency standard, and the components of the catalyst material within the size range of 0.2 µm or more and 1.5 µm or less. Can be applied.

FIG. 2 is a conceptual view illustrating an example of forming irregularities on the metal substrate 10 by using a roller 50. Cold rolling for forming minute protrusions or grooves having a height, depth or width of 0.2 μm or more and 1.5 μm or less. As shown in FIG. 2, unevenness | corrugation can be formed uniformly in the whole surface, rotating the roller (work roll) 50 in the state which pressed the surface of the flat metal substrate 10. FIG.

Roller dies made of metal or metal composite ceramics, which are made of metal or metal composite ceramics, which are made of brass or graphite, which are easy to process, to precisely die, and then pressurize the metal substrate 10 by plasticity. The roller can be produced by electrical discharge machining by bringing into contact with the workpiece and causing discharge to occur in the contact gap.

On the other hand, as shown in Figure 3, by the shot blast processing (shot blast) to the outer peripheral surface of the roller 50 or the surface of the metal substrate 10, the height, depth or width of less than 2㎛ 1.5㎛ Branches may evenly form fine protrusions or grooves.

When shot peening is applied to metal materials, work hardening can be applied to the surface to increase fatigue strength and fatigue life, and even when manufacturing metal substrates of the same thickness, high strength can be realized compared to flat metal base materials without irregularities. It is possible to reduce the weight.

The metal substrate 10 having the irregularities formed thereon is bent or brazed into a corrugated plate, and then inserted and brazed in an outer cylinder, impregnation into an apparatus having the catalyst 20 in a slurry state, or The catalyst 20 is coated using a suction device connected to one side of a vacuum.

Table 2 below summarizes the results of experiments on nitrogen oxide reduction efficiency of the first embodiment of the marine exhaust gas filter in the temperature range of 150 ~ 200 ℃.

Experimental conditions are N ₂ balance, NO 500 ppm, NH ₃ 500 ppm, O ₂ 11%, Water 10%, SV (Stay Velocity) 40000 h ⁻¹ .

Temp. [℃]

150
155
160
165
170
175
180
185
190
195
200
DeNOx [%]

65
72
80
85
89
92
94
97
98
100
100

According to the first embodiment of the ship exhaust gas filter in Table 2 it can be seen that implement the nitrogen oxide reduction efficiency of more than 90% at 175 ℃ or more, to implement the nitrogen oxide reduction efficiency of 100% at 195 ℃ or more You can see that.

For the actual vessel SV (space velocity) because it is 5,000 ~ 10,000h ^-1 degree, at the time of the actual ship station, compared to SV 40000 h ^-1 of the experimental conditions, increasing the reaction time between the reaction gas and the catalyst sites and probabilistic As the number of gases that can be reacted with increases, the nitrogen oxide reduction efficiency is more improved than that shown in [Table 2].

The second embodiment of the marine exhaust gas filter is a first embodiment of the low temperature active catalyst for the marine exhaust gas filter, or the marine exhaust gas filter on the surface of a ceramic substrate (eg, Cordierite substrate). It has a configuration in which the catalyst prepared by the first embodiment of the method for preparing a low temperature active catalyst for coating is coated.

Table 3 summarizes the results of experiments to reduce the nitrogen oxides of the second embodiment of the marine exhaust gas filter in the temperature range of 150 ~ 200 ℃, the following experimental conditions of the first embodiment of the marine exhaust gas filter Same as experimental conditions.

Temp. [℃]

150
155
160
165
170
175
180
185
190
195
200
DeNOx [%]

72
75
86
89
92
94
95
97
98
98
98

According to the second embodiment of the ship exhaust gas filter in Table 3 it can be seen that to implement the nitrogen oxide reduction efficiency of more than 90% at 170 ℃ or more, to achieve a nitrogen oxide reduction efficiency of 100% above 200 ℃ It can be predicted.

For the actual vessel SV (space velocity) because it is 5,000 ~ 10,000h ^-1 degree, the actual vessel at the time of operation, the table 3 is compared with the SV 40000 h ^-1 experimental conditions of experiments, the reaction between the gas and the catalyst sites in the As the reaction time increases and the gas that can react probabilisticly also increases, the nitrogen oxide reduction efficiency is further improved than the performance shown in [Table 3].

The third, fourth, fifth, and sixth embodiments of the ship exhaust gas filter described below are also experimented under the same conditions as the first and second embodiments of the ship exhaust gas filter. Compared with the experimental results of 7], it is apparent that the nitrogen oxide reduction efficiency is further improved when the ship is actually operated, and the description thereof will be omitted below.

Next, the second embodiment of the low temperature active catalyst for ship exhaust gas filter, the second embodiment of the method for producing the low temperature active catalyst for ship exhaust gas filter and the third and fourth embodiments of the ship exhaust gas filter will be described. Shall be.

Hereinafter, the same construction, principle, and operation as those described in the detailed description of the first embodiment of the low temperature active catalyst, the first embodiment of the preparation method, and the first and second embodiments of the ship exhaust gas filter to which the same is applied. Repetitive description of the detailed description will be omitted.

The second embodiment of the low temperature active catalyst for the ship exhaust gas filter comprises 1 to 3% by weight of Cu, 1 to 5% by weight of Mn, and 10 to 20% by weight of aluminasol based on the zeolite support FeZSM5 and FeZSM5.

In the preparation of the second embodiment of the low temperature active catalyst, in the first step, in the first step, DI water and Cu precursor in 1 to 5% by weight relative to the FeZSM5 Further stirring the Mn precursor of, in the third step, 10 to 20% by weight of the Aluminasol with respect to FeZSM5 has a difference.

The third embodiment of the ship exhaust gas filter is a second embodiment of the low temperature active catalyst for the ship exhaust gas filter on the surface of the metal substrate 10, or the method for manufacturing the low temperature active catalyst for the ship exhaust gas filter. It has a configuration in which the catalyst prepared in Example 2 is coated.

Table 4 below summarizes the results of experiments on nitrogen oxide reduction efficiency of the third embodiment of the ship exhaust gas filter in the temperature range of 150 ~ 200 ℃.

Temp. [℃]

150
155
160
165
170
175
180
185
190
195
200
DeNOx [%]

78
80
81
82
84
85
86
89
91
94
97

In Table 4, according to the third embodiment of the marine exhaust gas filter, it can be seen that the nitrogen oxide reduction efficiency of 90% or more is implemented at 190 ° C or higher, and the nitrogen oxide reduction efficiency is 100% or higher at 200 ° C or higher. It can be predicted.

The fourth embodiment of the marine exhaust gas filter is a second embodiment of the low temperature activated catalyst for the marine exhaust gas filter on the surface of the ceramic substrate, or the second embodiment of the low temperature active catalyst production method for the marine exhaust gas filter. It has a configuration in which the catalyst prepared by coating.

Table 5 below summarizes the results of experiments on nitrogen oxide reduction efficiency of the second embodiment of the ship exhaust gas filter in the temperature range of 150 ~ 200 ℃.

Temp. [℃]

150
155
160
165
170
175
180
185
190
195
200
DeNOx [%]

83
86
87
88
89
94
97
99
100
100
100

According to the fourth embodiment of the ship exhaust gas filter in Table 5 it can be seen that implement the nitrogen oxide reduction efficiency of more than 90% at 170 ℃ or more, to implement the nitrogen oxide reduction efficiency of 100% at 190 ℃ or more You can see that.

Next, the third embodiment of the low temperature active catalyst for ship exhaust gas filter, the third embodiment of the method for producing the low temperature active catalyst for ship exhaust gas filter, and the fifth and sixth embodiments of the ship exhaust gas filter will be described. Let's do it.

The third embodiment of the low temperature active catalyst for ship exhaust gas filter is based on the zeolite carrier FeZSM5, FeZSM5 1 to 3% by weight, Mn 1 to 5% by weight, Ca 1 to 5% by weight, Aluminasol 10 to 20% by weight It is composed of%.

In preparing a third embodiment of the low temperature active catalyst, the first step is a step of stirring the DI water, Cu precursor, Mn precursor compared to the first and second embodiments of the low temperature active catalyst Step 1-1, and has a difference consisting of the first and second steps of stirring the DI water, Mn precursor, Ca precursor.

In the second step, the stirred material of the first-first step, the stirred material of the first-second step, and FeZSM5 are stirred together, and the first-first step and the first-second step are 30 ~. 50 min, the second step is 3 to 5 hrs, and the third step is 1 to 2 hrs.

The Mn precursor contains 1 to 5% by weight based on the FeZSM5, in the first-first step and the first-second step, the part is stirred with DI water, Cu precursor and the DI water, Ca precursor and stirring After being divided into each of the remaining to be stirred, the mixture is mixed together in the second step to have a composition of 1 to 5% by weight relative to the FeZSM5.

The fifth embodiment of the ship exhaust gas filter is a third embodiment of the low temperature active catalyst for the ship exhaust gas filter on the surface of the metal substrate 10, or the method for manufacturing the low temperature active catalyst for the ship exhaust gas filter. It has a configuration in which the catalyst prepared according to the third embodiment is coated.

[Table 6] below summarizes the results of experiments on nitrogen oxide reduction efficiency of the third embodiment of the ship exhaust gas filter in the temperature range of 150 ~ 200 ℃.

Temp. [℃]

150
155
160
165
170
175
180
185
190
195
200
DeNOx [%]

91
92
95
98
99
100
100
100
100
100
100

According to the fifth embodiment of the ship exhaust gas filter in Table 6 it can be seen that implement the nitrogen oxide reduction efficiency of more than 90% at 150 ℃ or more, to implement the nitrogen oxide reduction efficiency of 100% at 175 ℃ or more You can see that.

The sixth embodiment of the ship exhaust gas filter is a third embodiment of the low temperature active catalyst for ship exhaust gas filter, or the third embodiment of a method for manufacturing the low temperature active catalyst for ship exhaust gas filter on the surface of a ceramic substrate. It has a configuration in which the catalyst prepared by coating.

[Table 7] below summarizes the results of experiments on nitrogen oxide reduction efficiency of the third embodiment of the ship exhaust gas filter in the temperature range of 150 ~ 200 ℃.

Temp. [℃]

150
155
160
165
170
175
180
185
190
195
200
DeNOx [%]

95
97
98
98
98
99
100
100
100
100
100

According to the sixth embodiment of the ship exhaust gas filter in Table 7 it can be seen that implement the nitrogen oxide reduction efficiency of more than 95% at 150 ℃ or more, to implement the nitrogen oxide reduction efficiency of 100% at 180 ℃ or more You can see that.

According to Tables 1 to 7, it can be seen that the first embodiment of the low temperature active catalyst for ship exhaust gas filter <second embodiment <the third embodiment is excellent in nitrogen oxide removal efficiency, In the case of using a metal substrate, the nitrogen oxide removal efficiency is known to be lower than that of the ceramic substrate. However, by using the metal substrate 10 having the uneven surface as described above, the nitrogen oxide removal efficiency is the same as that of the ceramic substrate. You can see that we implement

A promoter is a substance that is added to a solid catalyst to increase the activity of the catalyst in a chemical reaction. The promoter itself does not act as a catalyst, but some promoters interact with the active component of the catalyst to produce electrons from the active solid component. By changing the structure or crystal structure, the chemical effects on the catalyzed material can be changed.

If the cocatalyst metal component is excessively used, the active surface of the metal may be deposited rather than uniformly dispersed on the zeolite carrier, thereby degrading the performance of the active surface of the metal. Shows performance.

The applicant sets the criterion for determining the superiority of the catalyst performance at low temperature activity, and is limited to the cocatalyst composition ratio as disclosed in the first, second and third embodiments of the low temperature active catalyst for ship exhaust gas filter, which is considered to be the most preferable. However, this suggests a preferred content example and can be implemented in other compositions according to the operating conditions of the ship.

As a promoter, Cu and Mn are materials capable of activating low temperatures, and can actively induce oxidation and reduction reactions at low temperatures. As a result of the applicant's research and experiments, it is confirmed that a specific mixing ratio having excellent active properties exists. Ca can not only enhance the resistance to sulfur, but also stabilize the structure of Cu, Mn and FeZSM5, thereby securing catalyst performance in terms of stability and durability.

Table 8 below shows a metal substrate coated with a third embodiment of a conventional marine extrusion catalyst filter, a low temperature activated catalyst for marine exhaust gas filter (a fifth embodiment of the marine exhaust gas filter), and a ceramic substrate (the above The results of catalyst adhesion evaluation in Example 6 of the ship exhaust gas filter are summarized.

Each specimen was individually immersed in a beaker containing water, and each beaker was placed in an ultrasonic cleaning apparatus and sonicated at 40 MHz for 3 min. Then, each sample was sufficiently dried for 24 hrs and weighed to determine Loss amount and adhesion were calculated.

Conventional Extrusion Catalytic Filter

Fifth Embodiment (Metal Substrate)
Sixth Embodiment (Ceramic Substrate)
Attachment
result


0%

95%

45%

The adhesion test evaluates the binding force between the catalyst and the substrate. The weaker the binding force of the catalyst, the less catalyst remains attached to the substrate and the reaction site that can remove the nitrogen oxides decreases. It can be judged that the oxide removal performance falls.

Existing extrusion catalyst filter <ceramic substrate coated with a low temperature active catalyst according to an embodiment of the present invention <can be confirmed that the adhesion is excellent in the order of the metal substrate coated with a low temperature active catalyst according to an embodiment of the present invention.

In the implementation of the excellent adhesion as described above, the main characteristics of the surface characteristics of the metal substrate, such as the adoption of the sol-type Aluminasol having a needle-like structure of Alumina single component and its proper composition ratio, uneven structure Based.

The present invention has been described with reference to preferred embodiments of the present invention, but the present invention is not limited to these embodiments, and the claims and detailed description of the present invention together with the embodiments in which the above embodiments are simply combined with existing known technologies. In the present invention, it can be seen that the technology that can be modified and used by those skilled in the art are naturally included in the technical scope of the present invention.

10: metal substrate 20: catalyst
50: Roller

Claims (26)

In the catalyst for removing nitrogen oxide contained in the exhaust gas,
Zeolite support FeZSM5, Ca 1-5% by weight, Aluminasol 5-20% by weight relative to FeZSM5;
Low temperature active catalyst for exhaust gas filter, characterized in that comprising a.
The method of claim 1,
Mn 1-5 wt% with respect to FeZSM5;
Low temperature active catalyst for exhaust gas filter, characterized in that further comprises.
The method of claim 1,
Mn 1-5 wt%, Cu 1-3 wt% based on the FeZSM5;
Low temperature active catalyst for exhaust gas filter, characterized in that further comprises.
The method of claim 1,
The Aluminasol,
Low temperature active catalyst for exhaust gas filter, characterized in that the sol (sol) having a needle-like structure of Alumina monocomponent.
In the method for producing a catalyst for removing nitrogen oxide contained in the exhaust gas,
A first step of stirring DI water and Cu precursor;
A second step of stirring the stirred material of the first step and FeZSM5, wherein the Cu is 1 to 3% by weight relative to the FeZSM5; And
A third step of stirring the aluminasol and the aluminasol of the second step, wherein the aluminasol is stirred at 5 to 20% by weight with respect to the FeZSM5;
, &Lt; / RTI &gt;
In the first step,
1-5 wt% of Mn precursor and 1-5 wt% of Ca based on FeZSM5 are further stirred.
The method of claim 5,
It is made in a temperature environment of 50 ~ 80 ℃, FeZSM5: DI water is a low-temperature active catalyst manufacturing method for an exhaust gas filter, characterized in that having a weight ratio of 3 to 5: 6-8.
The method of claim 5,
The first step is 30 min, the second step is 1 to 3 hrs, the third step is a low temperature active catalyst manufacturing method for an exhaust gas filter, characterized in that made for 1 to 2 hrs.
The method of claim 5,
In the first step,
Method for producing a low temperature active catalyst for an exhaust gas filter, characterized in that for stirring 1 to 5% by weight of Mn precursor with respect to FeZSM5.

delete 9. The method of claim 8,
In the first step,
Step 1-1 to stir the DI water and Cu precursor, Mn precursor; And
Step 1-2 of stirring the DI water, Mn precursor, Ca precursor;
Low temperature active catalyst production method for an exhaust gas filter, characterized in that comprises a.
The method of claim 10,
The second step comprises:
Method for producing a low temperature active catalyst for an exhaust gas filter, characterized in that the stirring of the first-first stage, the stirred of the first-second stage, FeZSM5.
The method of claim 11,
Low temperature active catalyst for exhaust gas filter, characterized in that the first step, the first step is 30 ~ 50 min, the second step is 3 ~ 5 hrs, the third step is 1 ~ 2 hrs Manufacturing method.
An exhaust gas, which is formed by coating a metal substrate or a ceramic substrate with a low temperature active catalyst for exhaust gas filter according to claim 1 or a catalyst produced by the low temperature active catalyst for exhaust gas filter according to claim 5. Gas filter.
The method of claim 13,
The metal substrate,
An exhaust gas filter, characterized in that irregularities are formed on the surface to enlarge the coating area per unit area of the catalyst compared to the flat plate.
15. The method of claim 14,
Unevenness of the metal substrate,
An exhaust gas filter having a height, a depth, or a width of less than or equal to 0.2 μm and less than or equal to 1.5 μm, and formed uniformly over the metal substrate 10.
15. The method of claim 14,
Unevenness of the metal substrate,
The catalyst having a viscosity that the edge portion is an obtuse angle in the state attached to the flat plate, the exhaust gas filter, characterized in that formed in size and density to achieve an acute angle due to the reduction of the surface tension in the state attached to the metal substrate .
In the catalyst for removing nitrogen oxide contained in the exhaust gas,
Zeolite carrier FeZSM5, 1-3 wt% Cu, 5-20 wt% Aluminasol based on FeZSM5;
And a control unit,
It is used in the temperature range of 190 ~ 200 ℃, low temperature active catalyst for ship exhaust gas filter, characterized in that to implement the nitrogen oxide reduction efficiency of more than 90% in the temperature range.
18. The method of claim 17,
Mn 1-5 wt% with respect to FeZSM5;
Low temperature active catalyst for ship exhaust gas filter, characterized in that further comprises.
In the method for producing a catalyst for removing nitrogen oxide contained in the exhaust gas,
A first step of stirring DI water and Cu precursor;
A second step of stirring the stirred material of the first step and FeZSM5, wherein the Cu is 1 to 3% by weight relative to the FeZSM5; And
Stirring the aluminasol and the aluminasol of the second step, wherein the aluminasol is stirred at 5 to 20% by weight with respect to the FeZSM5;
And a control unit,
It is used in a temperature range of 190 ~ 200 ℃, low temperature active catalyst manufacturing method for a ship exhaust gas filter, characterized in that to implement a nitrogen oxide reduction efficiency of more than 90% in the temperature range.
20. The method of claim 19,
It is made in a temperature environment of 50 ~ 80 ℃, FeZSM5: low temperature active catalyst production method for ship exhaust gas filter, characterized in that DI water has a weight ratio of 3 to 5: 6 to 8.
20. The method of claim 19,
The first step is 30 min, The second step is 1 to 3 hrs, The third step is a low temperature active catalyst manufacturing method for a ship exhaust filter, characterized in that made for 1 to 2 hrs.
20. The method of claim 19,
In the first step,
Method for producing a low temperature active catalyst for a ship exhaust gas filter, characterized in that further stirring 1 to 5% by weight of Mn precursor with respect to FeZSM5.
A metal substrate or a ceramic substrate is formed by coating a catalyst prepared by the low temperature active catalyst for ship exhaust gas filter according to claim 17 or the low temperature active catalyst for ship exhaust gas filter according to claim 19. Marine exhaust gas filter.
24. The method of claim 23,
The metal substrate,
A marine exhaust gas filter, characterized in that irregularities are formed on the surface to enlarge the coating area per unit area of the catalyst compared to the flat plate.
25. The method of claim 24,
Unevenness of the metal substrate,
A ship exhaust gas filter having a height, depth or width of 0.2 μm or more and 1.5 μm or less and uniformly formed throughout the metal substrate.
25. The method of claim 24,
Unevenness of the metal substrate,
The catalyst having a viscosity at which the edge portion forms an obtuse angle in a state of being attached to a flat plate is formed in a size and density to form an acute angle due to a decrease in surface tension in a state of being attached to the metal substrate. filter.

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