KR102349738B1 - Manufacturing method of Nickel based active catalysts - Google Patents

Abstract

Mixing and stirring the nickel-based active metal and distilled water (S210); Mixing the Zr-Al support and drying at a low temperature of 60 ~ 70 ℃ (S220); maintaining the dried catalyst at a second high temperature higher than the low temperature (S230); and maintaining the dried catalyst at a third high temperature higher than the second high temperature (S240).

Description

Nickel-based active catalyst manufacturing method {Manufacturing method of Nickel based active catalysts}

The present invention relates to a catalyst containing an active metal, and more particularly, to a method for preparing a nickel-based active catalyst and the catalyst.

Hazardous waste gas emitted from the semiconductor manufacturing process is emitted in a very diverse manner according to each process, and most of it is highly volatile and is required to be removed because it is composed of components that are harmful to the human body or have a high global warming potential. Among them, perfluorocompound (PFC), which is a perfluorinated compound mainly discharged from etching and deposition (CVD) processes of semiconductor processes, is very stable and difficult to remove. PFCs are more stable than CFCs (chlorofluorocompounds) used as refrigerants, have a large global warming potential, and have a very long decomposition time, so when released, they accumulate in the atmosphere. PFCs emitted from semiconductor processes are increasing at a high rate every year.

Therefore, since the effect of PFC generation on global warming is increasing, each country is gradually strengthening the regulation on PFC. Attempts have been made to develop a new alternative gas to reduce PFC emissions. However, as a gas used for etching silicon substrates during the semiconductor manufacturing process, _{an alternative gas that is more efficient than CF 4} and superior in productability has not been proposed. _{Accordingly, CF 4} is being used in most semiconductor manufacturing processes.

Various technologies for removing PFCs, particularly carbon-based PFCs, are under development, and can be divided into the field of separation and recovery using PSA and separation membrane and the field of decomposition and removal using plasma, combustion or catalyst.

The catalytic decomposition method is a technique for decomposing difficult-to-decompose PFC at a low temperature of 800° C. or less using a catalyst and water vapor. The catalytic method can significantly lower the decomposition temperature, thereby bringing many advantages. For example, if decomposition is performed at a low temperature of 800° C. or less, it has the advantage of reducing operating costs and facilitating securing the durability of the system according to continuous operation, suppressing the generation of thermal NOx resulting from N2 present in the exhaust gas, It has the advantage of greatly reducing corrosion. On the other hand, there is an advantage in that the size of the scrubber can be greatly reduced by increasing the reaction activity of the catalyst, so that it can be miniaturized.

However, the catalytic decomposition method has a problem in that the catalyst must be replaced periodically because halogen compounds such _{as HF and F 2 generated after the reaction rapidly deteriorate the catalyst performance.} Various studies have been conducted, such as returning the catalyst to the original catalyst state by contacting it with water vapor, or forming a film on the catalyst surface.

In the prior art Japanese Patent Laid-Open Nos. Hei 11-70332 and Hei 10-46824, a catalyst was prepared in the form of a composite oxide of aluminum and a metal component containing at least one or more of various transition metals such as Zn, Ni, Ti, Fe, etc. inside aluminum oxide to decompose perfluorinated compounds, and US Patent Nos. 6,023,007 and 6,162,957 disclose that various types of metal phosphate catalysts can be used as catalysts for decomposing perfluorinated compounds. However, as described above, aluminum phosphate in the form of a multi-component composite oxide to which a metal component is added is not only complicated in the manufacturing process, but also disadvantageous in terms of economy, and the possibility of long-term use is also opaque, so that the catalytic activity can be maintained for a long time. There is still a need for the development of a method that can simply and economically prepare a catalyst with

1. Republic of Korea Patent Application No. 10-1998-0023130 (Decomposition treatment method of fluorine-containing compounds, catalyst and decomposition treatment apparatus), 2. Korean Patent Application No. 10-2017-0025748 (acid-resistant catalyst for decomposition of perfluorinated compounds and uses thereof); 3. Japanese Patent Application No. 2002-247952 (Method for decomposing perfluoro compounds, decomposition catalyst and treatment apparatus).

Therefore, the present invention has been devised to solve the above problems, and the problem to be solved by the present invention is to prepare a nickel-based active catalyst characterized in that 10% of nickel acting as an active point is supported in the PFCs active catalyst to provide a way

However, the technical problems to be achieved in the present invention are not limited to the technical problems mentioned above, and other technical problems that are not mentioned are clearly to those of ordinary skill in the art to which the present invention belongs from the description below. can be understood

In order to achieve the above technical task, the step of mixing and stirring the nickel-based active metal and distilled water (S210); Mixing the Zr-Al support and drying at a low temperature of 60 ~ 70 ℃ (S220); maintaining the dried catalyst at a second high temperature higher than the low temperature (S230); and maintaining the dried catalyst at a third high temperature higher than the second high temperature (S240); there is provided a nickel-based active catalyst manufacturing method comprising:

In addition, in the stirring step (S210), 10 to 30 wt% of the active metal and 30 to 40 ml of the distilled water are mixed.

Further, the second high temperature is in the range of 450°C to 550°C, and the third high temperature is in the range of 650°C to 750°C.

In addition, the Zr-Al support, 3 to 15 wt% of zirconium oxynitrate solution and preparing a boehmite solution, respectively (S110, S120); stirring the zirconium oxynitrate solution and the boehmite solution (S140); Aging the support in the form of a gel while stirring (S150); drying the aged support in a first high temperature state that is a temperature between the low temperature and the second high temperature (S160); And after sieving the dried support, maintaining it at a second high temperature (S170); can be prepared by.

In addition, the stirring step (S140) of the support is stirred for 3 to 5 hours.

In addition, the stirred solution in the stirring step (S140) of the support has a pH of 3.

In addition, the aging step (S150) is aged for 36 to 60 hours.

Also, the first high temperature is in the range of 90°C to 110°C.

In addition, the preparation steps (S110, S120) of the support further include a step (S130) of preparing a solution of the nickel-based active metal, and in the stirring step (S140) of the support, the solution of the nickel-based active metal can be stirred together. have.

In addition, mixing the prepared Zr-Al support and a solution of the nickel-based active metal and drying at a low temperature (S180); and maintaining at a second high temperature (S190).

The object of the present invention as described above can also be achieved by the Zr-Al support prepared by the above-described manufacturing method.

The object of the present invention as described above can also be achieved by the nickel-based active catalyst prepared by the above-described manufacturing method.

According to an embodiment of the present invention, there are advantages in that the manufacturing process is simple, economical, and long-term use is possible.

In addition, due to the nickel-based active catalyst, there is an effect that is a catalyst having a durability that can be maintained for a long time catalytic activity.

However, the effects obtainable in the present invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those of ordinary skill in the art to which the present invention belongs from the following description. will be able

The following drawings attached to this specification illustrate preferred embodiments of the present invention, and serve to further understand the technical spirit of the present invention together with the detailed description of the present invention to be described later, so the present invention is described in such drawings It should not be construed as being limited only to
1 is a graph showing the performance results for each content _{of ZrO 2 in} the support in an embodiment of the present invention;
2 is a graph showing performance results for each active metal Nidml content in an embodiment of the present invention;
3 is a graph showing performance results for each type of co-catalyst in one embodiment of the present invention;
4 is a graph showing performance results for each content of a cocatalyst in an embodiment of the present invention;
5 is a graph showing performance results for each method of supporting a cocatalyst in an embodiment of the present invention;
6 is a graph showing the performance results according to the space velocity change of the Ni-based active catalyst prepared according to an embodiment of the present invention;
7 is a graph showing the performance results according to the moisture content of the Ni-based active catalyst prepared according to an embodiment of the present invention;
8 is a graph showing the long-term durability evaluation results of the Ni-based active catalyst prepared according to an embodiment of the present invention;
9 is a flowchart showing a method for manufacturing a Zr-Al support used in the present invention;
10 is a flowchart illustrating a method for preparing a nickel-based active catalyst according to an embodiment of the present invention.

Hereinafter, with reference to the accompanying drawings, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, since the description of the present invention is merely an embodiment for structural or functional description, the scope of the present invention should not be construed as being limited by the embodiment described in the text. That is, since the embodiment may have various changes and may have various forms, it should be understood that the scope of the present invention includes equivalents capable of realizing the technical idea. In addition, since the object or effect presented in the present invention does not mean that a specific embodiment should include all of them or only such effects, it should not be understood that the scope of the present invention is limited thereby.

The meaning of the terms described in the present invention should be understood as follows.

Terms such as “first” and “second” are for distinguishing one component from another, and the scope of rights should not be limited by these terms. For example, a first component may be termed a second component, and similarly, a second component may also be termed a first component. When a component is referred to as being “connected to” another component, it may be directly connected to the other component, but it should be understood that other components may exist in between. On the other hand, when it is mentioned that a certain element is "directly connected" to another element, it should be understood that the other element does not exist in the middle. Meanwhile, other expressions describing the relationship between elements, that is, "between" and "between" or "neighboring to" and "directly adjacent to", etc., should be interpreted similarly.

The singular expression is to be understood to include the plural expression unless the context clearly dictates otherwise, and terms such as "comprise" or "have" are not intended to refer to the specified feature, number, step, action, component, part or any of them. It is intended to indicate that a combination exists, and it should be understood that it does not preclude the possibility of the existence or addition of one or more other features or numbers, steps, operations, components, parts, or combinations thereof.

All terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs, unless otherwise defined. Terms defined in general used in the dictionary should be interpreted as having the same meaning in the context of the related art, and cannot be interpreted as having an ideal or excessively formal meaning unless explicitly defined in the present invention.

Preparation of support

9 is a flowchart illustrating a method for manufacturing a Zr-Al support used in the present invention. As shown in FIG. 9, first, a target content of the zirconium oxynitrate reagent (in the present invention 3 to 15 wt% ZrO ₂ , preferably 7 to 8 wt% ZrO ₂ , and more preferably is 7.5 wt% ZrO ₂ ) by stirring at a ratio of 40 to 60 ml of distilled water to dissolve (S110). At this time, if there is an active metal to be added (eg nickel), it is dissolved together (S130), and in the case of an amount of water that is not sufficiently dissolved, the active metal is separately dissolved using about 40 ml of distilled water and then added together in step S140.

In addition, the boehmite is mixed with distilled water using an impeller stirrer, and at this time, the boehmite is prepared by sufficiently stirring until it is dissolved without agglomerated parts (S120).

Then, the ionized zirconium oxynitrate solution and the boehmite solution are slowly poured and mixed for 4 hours (S140). At this time, the impeller agitation should be done vigorously, and in this example, it was stirred at 400 rpm. Also, the pH of the solution was maintained at about 3.0. In addition, the solution of the active metal prepared in step S130 may be stirred together.

Then, after stirring, the solid support in the form of a gel is stored in a desiccator without a change in temperature for about 48 hours (avoid direct sunlight or in a dark room) and aged (S150).

Then, the aged support is sufficiently dried in an oven at a first temperature (105 ° C.) so that moisture does not exist inside the support (S160).

Then, after sieving to a size of 12 to 25 mesh for uniform heat treatment of the dried support, it is maintained at a second high temperature (500° C.) for about 3 hours (S170).

Then, optionally, when you want to separately coat the active metal on the prepared Zr-Al support, 40 ml of the active metal solution prepared in step S130 is mixed with the Zr-Al support in a round flask, and then at low temperature (65 ℃). Evaporation using a water bath (water bath) and an evaporator (evaporator) (S180).

Then, the second high temperature (500 ℃) is maintained for about 3 hours (S190) to complete the Zr-Al support (S195).

Preparation of active catalyst

10 is a flowchart illustrating a method for preparing a nickel-based active catalyst according to an embodiment of the present invention. As shown in FIG. 10, first, the impregnation method is used, that is, 10-30 wt% of active metal and 30-40 ml of distilled water are mixed and stirred (S210).

Then, when the active metal is sufficiently dissolved, the Zr-Al support and the active metal solution are mixed in a round flask, and then evaporated to dryness using a low temperature (65 ° C) water bath and an evaporator. make it (S220). At this time, the active metal may be prepared by mixing one or more.

Then, the dried granular catalyst is maintained for about 2 hours at a second high temperature (500 ° C.) in the square kiln (S230).

Then, it is continuously maintained at a third high temperature (700° C.) for about 2 hours to complete the final nickel-based activated catalyst (S250).

catalytic activity experiment

After fixing the content of the nickel-based active catalyst prepared according to an embodiment of the present invention according to the space velocity (4000, 6000, 8000 h ^-1 ), put it in an Inconel reactor and GC-TCD in a temperature range of 550 ° C to 700 ° C. The discharged unreacted CF ₄ was measured. At this time, the CF ₄ conversion rate was calculated as {1- (unreacted CF ₄ concentration/initial CF ₄ concentration)}*100.

(1) ZrO in the support ₂ Influence of content

In order to investigate the effect of the content of the Zr-Al support used in the preparation of the nickel-based active catalyst of the present invention, an experiment was conducted under the following conditions. Experimental conditions were 550℃ ~ 700℃, 300 cc/min flow, 1,000 ppm CF ₄ /N ₂ balance, 8 v/v% H ₂ O, and space velocity of 4,000 h ^-1 .

Here, it was named as Zr-Al, but the actual content _{was calculated as ZrO 2} -Al ₂ O _{3 . The results of mixing ZrO 2} in various amounts, which are essential when manufacturing the support using the sol-gel method, are [Table 1] ] is the same as And, Figure 1 is a graph showing the performance results for each content _{of ZrO 2 in} the support in an embodiment of the present invention.

Al ₂ O ₃ 3% Zr-Al 7.5% Zr-Al 12% Zr-Al 15% Zr-Al 550 38.15 50.45 53.3083 45.52 32.90 600 37.57 72.52 83.7025 67.88 39.16 650 43.92 100.00 100.00 88.17 57.99 700 49.20 100.00 100.00 100.00 70.05

As shown in [Table 1] and FIG. 1 , 7.0% to 8.0%, most preferably 7.5% of ZrO ₂ , showed the best CF ₄ activity. All catalysts tested thereafter were prepared using a 7.5% Zr-Al support.

(2) Effect of active metal content

In order to investigate the effect of the content of the active metal (Ni) used in the preparation of the nickel-based active catalyst of the present invention, an experiment was conducted under the following conditions. Experimental conditions were 550℃ ~ 700℃, 300 cc/min flow, 1,000 ppm CF ₄ /N ₂ balance, 8 v/v% H ₂ O, space velocity 4,000 h ^-1 , support: 7.5% Zr-Al. The experimental results according to the change in the content of the active metal are shown in [Table 2] and FIG. 2 is a graph showing performance results for each active metal Nidml content in an embodiment of the present invention.

0% Ni 5% Ni 10% Ni 20% Ni 30% Ni 550 36.4100 46.4510 53.3083 41.2500 26.4723 600 79.3625 79.4193 83.7025 85.5803 59.9580 650 100.00 100.00 100.00 100.00 87.0050 700 100.00 100.00 100.00 100.00 100.00

As shown in [Table 2] and FIG. 2, as a result of loading nickel acting as an active point by various contents, the performance was reduced when a large amount was loaded, and in addition, 0 to 20% of the performance during nickel loading was achieved. Although the difference was insignificant, it was confirmed that 10% of the performance was improved to 92.1% at 600 °C when 10% of them were loaded.

(3) Effect of co-catalyst

In order to investigate the effect of the type of cocatalyst used in the preparation of the nickel-based active catalyst of the present invention, an experiment was conducted under the following conditions. Experimental conditions are 550℃ ~ 700℃, 300 cc/min flow, 1,000 ppm CF ₄ /N ₂ balance, 8 v/v% H ₂ O, space velocity 4,000 h ^-1 , support 3% Me - 7.5% Zr -Al. Experimental results according to the type of co-catalyst are shown in [Table 3] and FIG. 3 . 3 is a graph showing performance results for each type of cocatalyst in an embodiment of the present invention.

Cu P Mo W Ce 550 54.17 48.62 30.13 49.12 51.60 600 70.73 73.13 68.36 92.10 66.84 650 100.00 84.71 96.67 100.00 100.00 700 100.00 100.00 100.00 100.00 100.00

As shown in [Table 3] and FIG. 3, various active metals were added to the support in order to improve the thermal durability or acid sites of the support. Among them, the catalyst to which tungsten (W) was added _{showed excellent CF 4} activity of 92% at 600 °C.

(4) Effect of cocatalyst content

The cocatalyst used in the preparation of the nickel-based active catalyst of the present invention was limited to W, and an experiment was conducted under the following conditions to investigate the effect of the content of the cocatalyst. Experimental conditions are, 550℃ ~ 700℃, 300 cc/min flow, 1,000 ppm CF ₄ /N ₂ balance, 8 v/v% H ₂ O, space velocity 4,000 h ^-1 , support: X% W - 7.5% Zr -Al. When W was used as a co-catalyst, the experimental results according to the change in the content of the co-catalyst are shown in Table 4 and FIG. 4 . 4 is a graph showing performance results for each content of a cocatalyst in an embodiment of the present invention.

0% W 0.5% W 3% W 5% W 10% W 550 53.31 49.64 49.12 50.50 25.00 600 83.70 83.87 92.10 86.00 70.00 650 100.00 100.00 100.00 100.00 93.00 700 100.00 100.00 100.00 100.00 100.00

As shown in [Table 4] and FIG. 4, as a result of adding W, which showed the best catalytic activity, by various contents, the catalyst added with 3% showed the most excellent activity, and at this time, an excess of W was added. It was confirmed that the difference in performance was insignificant in the case of the catalysts added with 0.5% to 5% W except for the Ni/10% W-Zr-Al catalyst.

(5) Influence of the cocatalyst loading method

In order to investigate the effect of the supporting method of the cocatalyst used in the preparation of the nickel-based active catalyst of the present invention, an experiment was conducted under the following conditions. Experimental conditions are 550℃ ~ 700℃, 300 cc/min flow, 1,000 ppm CF ₄ /N ₂ balance, 8 v/v% H ₂ O, space velocity 4,000 h ^-1 , support: 7.5% Zr-Al.

The catalyst used in the present invention is divided into a support preparation step and an active metal coating step as follows, and steps are separated using “/” whenever heat treatment is performed.

ex1) M1/M2-support (M2 and support are mixed together and heat-treated, then heat-treated by mixing M1)

ex2) M1-M2/support (heat treatment by heat-treating the support separately, then mixing M1 and M2 with the heat-treated support)

ex3) M1/M2/Support (After heat-treating the support, heat it by mixing it with M2, and then mix it with M1 for heat treatment)

The experimental results are shown in [Table 5] and FIG. 5 . 5 is a graph showing performance results for each method of supporting a cocatalyst in an embodiment of the present invention.

Ni/W-Zr-Al Ni-W/Zr-Al Ni/W/Zr-Al 600 92.0983 87.6667 61.2004 650 100 91.5 87.7325 700 100 100 93.984

As shown in [Table 5] and FIG. 5, it was determined that the bonding state formed according to the supporting method would change, and as a result, when the active metal was mixed with the support, the best activity was shown. In addition, it showed the lowest activity when mixed with surface nickel, and when it was heat-treated alone, it was confirmed that the performance decreased by about 10%.

(6) Effect of operating conditions (space velocity, moisture content)

In order to investigate the effect of the operating conditions of the nickel-based active catalyst of the present invention, an experiment was conducted under the following conditions. Performance can be increased or decreased due to changes in contact time, etc., depending on the operating conditions of operating the system, not the inherent properties of the catalyst, so the performance was compared according to the typical operating conditions such as space velocity and water content. The first experimental condition (change in space velocity) was 550℃ ~ 700℃, 300 cc/min flow, 1,000 ppm CF ₄ /N ₂ balance, 8 v/v% H ₂ O, space velocity 2,000 ~ 8,000 h ^-1 , Catalyst: 10% Ni/3% W - 7.5% Zr-Al. The experimental results of the first experimental conditions are shown in [Table 6] and FIG. 6 . 6 is a graph showing the performance results according to the space velocity change of the Ni-based active catalyst prepared according to an embodiment of the present invention.

2000 h ^-1 4000 h ^-1 8000 h ^-1 550 93.18 49.12 18.38 600 100 92.10 52.60 650 100 100 75.13 700 100 100 90

The second experimental condition (change of moisture content) was 600℃, 300 cc/min flow, 1,000 ppm CF ₄ /N ₂ balance, 1~8 v/v% H ₂ O, space velocity 4,000 h ^-1 , catalyst: 10 % Ni / 3% W - 7.5% Zr-Al. The experimental results of the second experimental condition are shown in [Table 7] and FIG. 7 . 7 is a graph showing the performance results according to the moisture content of the Ni-based active catalyst prepared according to an embodiment of the present invention.

1 v/v% 5 v/v% 8 v/v% 600 66.42 78.75 92.10

As shown in [Table 6] and Figs. 6 and [Table 7] and Fig. 7, as the operating conditions were changed, the performance at 600 ° C. varied from 100% to 52.6%, and the moisture content was It was confirmed that the performance was improved when it was increased to 8 v/v%.

(7) Durability evaluation of nickel-based active catalyst (100 h long exposure)

In order to examine the durability of the nickel-based active catalyst of the present invention, an experiment was conducted under the following conditions. Experimental conditions are, 650℃, 300 cc/min flow, 1,000 ppm CF ₄ /N ₂ balance, 8 v/v% H ₂ O, space velocity 4,000 h ^-1 , catalyst: 10% Ni/3% W - 7.5% Zr-Al. The experimental results are shown in FIG. 8 . 8 is a graph showing the long-term durability evaluation results of the Ni-based active catalyst prepared according to an embodiment of the present invention. As shown in FIG. 8 , it was confirmed that the developed catalyst maintained 100% activity for 100 h or more at ^{4000 h −1 space velocity.}

The detailed description of the preferred embodiments of the present invention disclosed as described above is provided to enable any person skilled in the art to make and practice the present invention. Although the above has been described with reference to preferred embodiments of the present invention, it will be understood by those skilled in the art that various modifications and changes can be made to the present invention without departing from the scope of the present invention. For example, those skilled in the art can use each configuration described in the above-described embodiments in a way in combination with each other. Accordingly, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

The present invention may be embodied in other specific forms without departing from the spirit and essential characteristics of the present invention. Accordingly, the above detailed description should not be construed as restrictive in all respects but as exemplary. The scope of the present invention should be determined by a reasonable interpretation of the appended claims, and all modifications within the equivalent scope of the present invention are included in the scope of the present invention. The present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein. In addition, claims that are not explicitly cited in the claims can be combined to form an embodiment or included as a new claim by amendment after filing.

Claims (13)

In the method for producing a nickel-based active catalyst used in _{CF 4 conversion reaction,}
Mixing and stirring the nickel-based active metal and distilled water (S210);
Mixing the Zr-Al support and drying at a low temperature of 60 ~ 70 ℃ (S220);
maintaining the dried catalyst at a second high temperature higher than the low temperature for 2 hours (S230); and
Including; maintaining the dried catalyst at a temperature of a third high temperature higher than the second high temperature for 2 hours (S240);
The stirring step (S210) is,
10 to 30 wt% of the active metal and 30 to 40 ml of distilled water are mixed,
The Zr-Al support,
Preparing 3 ~ 15 wt% of zirconium oxynitrate solution and boehmite solution, respectively (S110, S120);
stirring the zirconium oxynitrate solution and the boehmite solution (S140);
Aging the support in the form of a gel while stirring (S150);
drying the aged support in a first high temperature state that is a temperature between the low temperature and the second high temperature (S160); and
After sieving the dried support, maintaining it at the second high temperature (S170);
The first high temperature is in the range of 90°C to 110°C, the second high temperature is in the range of 450°C to 550°C, and the third high temperature is in the range of 650°C to 750°C. The method of claim 1,
The nickel-based active catalyst,
A method for producing a nickel-based active catalyst, characterized in that 3% tungsten (W), which is a cocatalyst showing _{CF 4} activity performance, is added to improve the thermal durability or acid site of the Zr-Al support. 3. The method of claim 2,
The nickel-based active catalyst,
Method for producing a nickel-based active catalyst, characterized in that the co-catalyst and the Zr-Al support are mixed together and heat-treated, and then heat-treated after the nickel-based active metal is mixed. delete delete The method of claim 1,
The stirring step (S140) of the support is a nickel-based active catalyst manufacturing method, characterized in that the stirring for 3 to 5 hours. The method of claim 1,
The method for producing a nickel-based active catalyst, characterized in that the stirred solution in the stirring step (S140) of the support is pH 3. The method of claim 1,
The aging step (S150) is a nickel-based active catalyst manufacturing method, characterized in that the aging for 36 hours to 60 hours. delete The method of claim 1,
The preparation steps (S110, S120) of the support are,
Further comprising the step (S130) of preparing a solution of the nickel-based active metal,
A method for producing a nickel-based active catalyst, characterized in that the solution of the nickel-based active metal is stirred together in the stirring step (S140) of the support. The method of claim 1,
mixing the prepared Zr-Al support and a solution of a nickel-based active metal and drying at the low temperature (S180); and
Maintaining at the second high temperature (S190); Nickel-based active catalyst manufacturing method, characterized in that it further comprises. delete A nickel-based active catalyst, characterized in that it is prepared by the method of any one of claims 1, 6, 7, 8, 10 and 11.

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