KR101467292B1 - Selective surface impregnation method for catalytic material with the repulsive force between hydrophilic and hydrophobic solvents and catalyst made thereof - Google Patents

Abstract

The present invention relates to a method for preparing a catalyst in which a catalytically active material is selectively supported or impregnated only on a surface of a catalyst particle by using mutual repulsion of a hydrophobic solvent and a hydrophilic solvent, and a solubility difference of the hydrophobic solvent and the hydrophilic solvent with respect to a metal salt precursor, and in which C3-C6 alcohols, such as propanol, butanol, pentanol, hexanol are used as the hydrophobic solvent. A catalytically active material or a precursor preparing a catalytically active material selectively supported or impregnated on only outside of a catalyst particle by: introducing the hydrophobic solvent to a catalyst support; drying the resultant under an appropriate condition; removing the hydrophobic solvent from some pores connected to outside of a catalyst particle; the hydrophilic solution occupies an empty space in which the hydrophobic solvent has disappeared by introducing a hydrophilic solution including a metal salt; and drying the resultant at a slow rate. Through this method, it is possible to prepare an egg-shell type catalyst in which a catalytically active material supported or impregnated only on an outside region of a catalyst particle.

Description

TECHNICAL FIELD The present invention relates to a method for selectively supporting a surface of a catalytically active material using a repulsive force between a hydrophilic solvent and a hydrophobic solvent and a catalyst prepared by the method.

The present invention relates to a method for effectively reducing a catalyst production cost by optimizing an amount of a noble metal catalyst supported or impregnated on a porous catalyst carrier in a catalyst production process. More specifically, It is possible to prevent the metal catalyst from being impregnated or impregnated into the pores near the center of the support which is difficult to participate in the catalytic reaction by selectively supporting or impregnating the metal catalyst or the catalyst only in the pores near the surface and the surface of the support, In the presence of a catalyst.

More specifically, by supplying a hydrophobic solvent and a hydrophilic solvent to the catalyst carrier, which is a microporous structure, the catalytic active material is subjected to most of the catalytic reaction using the repulsive force of the hydrophobic solvent and the hydrophilic solvent, And selectively impregnating or impregnating the surface of the resulting catalyst carrier and the region in the vicinity of the surface of the catalyst carrier.

Generally, in the case of a reaction proceeding under a reaction condition having a high space velocity, such as a steam-methane reforming reaction and a water-gas shift reaction, only the surface portion of the catalyst reacts with the catalyst And the interior of the catalyst particles is rarely used for catalytic reactions. In the Fischer-Tropsch reaction, when the catalyst particles having a size of 1-3 mm are used, the diffusion rate of the reactant, CO, in the supported or impregnated catalyst carrier is limited, and the generation rate and selectivity of the hydrocarbon having 5 or more carbon atoms are decreased do. In order to overcome such a problem, many researchers have reported a method for preparing a catalyst by selectively impregnating or impregnating a catalytically active substance only on the surface portion of the formed catalyst support, and a catalyst prepared as described above.

Open Patent Application No. 2010-0011687 relates to a process for preparing a catalyst for reforming carbon dioxide of methane and a process for modifying the catalyst using the same, wherein the silica mesopore molecular sieve carrier is impregnated with a nickel nitrate aqueous solution, A method of preparing a catalyst by carrying out a second step of carrying out a catalyst in an aqueous solution of a co-catalyst, followed by drying and calcining steps. The present invention is characterized in that the main catalyst and the cocatalyst are sequentially formed in one catalyst carrier. However, since the drying and calcination are carried out separately in each catalyst formation step, the production cost is increased, There is still a difficult problem to impregnate or impregnate.

Published Patent No. 2010-0011687

The present invention is characterized in that a catalyst active material is selectively carried or impregnated only on the surface of the porous catalyst carrier having a spherical or cylinder shape and in the vicinity of the surface thereof and the porous pores formed in the vicinity of the center of the catalyst carrier, The present invention relates to a method for preventing the catalyst active material from being carried or impregnated thereby to save the use of a catalytically active substance which is a valuable noble metal in the production of the catalyst particles.

In addition, the present invention provides a catalyst carrier which is a microporous structure, in which a hydrophobic solvent and a hydrophilic solvent are sequentially supplied to the inside of the catalyst carrier, and immobilization of the catalytically active substance by most of the catalytic reactions In the vicinity of the surface of the catalyst carrier and the surface of the catalyst carrier.

By controlling the degree of immiscibility of the hydrophobic solvent and the hydrophilic solvent and the conditions for removing the hydrophobic and / or hydrophilic solvent, only a specific region such as the vicinity of the surface in the entire pore region inside the catalyst carrier is selectively carried or impregnated with the catalytically active substance ≪ / RTI >

The selective surface loading or impregnation of the catalytically active material of the present invention comprises: preparing a catalyst support (S10) for preparing a spherical or cylindrical porous inorganic oxide as a catalyst support; A first immersion step (S100) of filling the internal pores of the catalyst carrier with a hydrophobic first solvent; A first drying step (S200) of removing the hydrophobic first solvent in the pores of the area below the surface of the catalyst support through a drying process to thereby leave the hydrophobic first solvent in the pores of the inner central region of the catalyst support; A second immersion step (S300) of immersing the catalytic active material or the precursor of the catalytic active material in a hydrophilic second solvent to prepare a hydrophilic aqueous solution and then immersing the catalyst carrier having undergone the first drying step in the hydrophilic aqueous solution; A second drying step (S400) for removing the first solvent remaining in the catalyst carrier and the proton-accepting solution; And a supporting or impregnating step (S500) of selectively forming only the catalyst active material or the precursor of the catalytically active material remaining after the second drying step on the surface of the catalyst carrier and only the inner pore region beneath the surface thereof through a firing or reduction process, Lt; / RTI >
The second step of immersing may be performed in a range of 1/5 to 1/2 of the distance from the surface area of the catalyst carrier from which the hydrophobic first solvent has been removed to the center of the catalyst carrier through the first drying step, Wherein the hydrophilic second solvent is water and the hydrophilic aqueous solution is an aqueous solution of a catalytically active substance or a precursor aqueous solution of a catalytically active substance, And the hydrophobic first solvent and the hydrophilic second solvent present in the pores are removed.
Preferably, the porous inorganic oxide used in the present invention is at least one or more selected from the group consisting of silica, alumina, titania, zirconia and ceria, and the catalyst carrier is immersed in the hydrophobic first solvent through the first immersion step, And the inner pores are filled with the hydrophobic first solvent.

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The drying temperature and the drying time in the first drying step are not particularly limited, but are selected from the range of 50 ° C lower to 50 ° C higher than the boiling point of the first hydrophobic hydrophobic solvent, and the drying time is 1 minute to 120 minutes If the drying temperature of the first drying step is too low or the drying time is short, the first hydrophobic hydrophilic solvent may not be sufficiently removed. If the drying temperature is too high or the drying time is long The amount of the hydrophobic first solvent to be removed is so large that the amount of the catalytically active substance impregnated becomes too large because the second solution as the aqueous solution can freely permeate and the amount of the catalytically active substance to be impregnated becomes too large, Since it is not possible to achieve the object of the present invention that the catalyst active material is limited to be supported only on the surface of the carrier particles, And it is not preferable because it may lower the effectiveness of such economic improvement.

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The precursor of the catalytically active substance or the catalytically active substance used herein is a metal salt or metal salt precursor of any one of platinum, ruthenium, rhodium, cobalt, nickel, and palladium. The first hydrophobic solvent used in the present invention is n-propanol, at least one selected from the group consisting of n-butanol, n-pentanol, n-hexanol, ethylene glycol, propylene glycol and their derivatives and isomers.

The hydrophobic first solvent and the hydrophilic second solvent existing in the inner pores of the catalyst carrier are removed by the second drying step, and the immersion time in the second immersion step is preferably in the range of 1 minute to 60 minutes Do. If the immersion time of the second immersion step is too short, the hydrophilic aqueous solution may not be sufficiently absorbed into the interior of the interior of the catalyst carrier particles, and if it is too long, the productivity may be lowered.

In addition, in the first immersion step, sonication may be performed as needed so that the hydrophobic first solvent can fill the inner pores of the catalyst carrier particles.

The catalyst prepared by the selective surface loading or impregnation method of the catalytically active substance using the repulsive force between the hydrophilic solvent and the hydrophobic solvent described above has a performance equal to or higher than that of the existing catalyst at a low cost, There is an effect that the catalytically active material can be selectively carried or impregnated only in a specific region such as the vicinity of the catalyst layer.

The method according to the present invention selectively supports or impregnates the catalytic active materials, such as platinum, ruthenium, rhodium, cobalt, nickel, etc., which occupy a large portion of the catalyst production cost, only on the surface of the catalyst carrier, And lowering the production cost of the catalyst.

In addition, when the present invention is used, various catalysts can be selectively carried or impregnated in a specific region in the pore of the catalyst carrier in the radial direction by controlling the immersion time and drying temperature of the hydrophobic solvent and the hydrophilic solvent, It is possible to design and produce composite catalysts.

FIG. 1 is a schematic view illustrating a method of selectively supporting or impregnating a catalytically active substance using a repulsive force between a hydrophilic solvent and a hydrophobic solvent of the present invention.
FIG. 2 is a diagram schematically illustrating a structural change of a catalyst carrier according to a method of selectively supporting or impregnating a catalytically active substance using a repulsive force between a hydrophilic solvent and a hydrophobic solvent of the present invention. FIG.
3 is a photograph of Examples 1-4 and Comparative Examples of the present invention.
4 is a photograph of the fifth embodiment of the present invention.

The present invention relates to a method of selectively supporting or impregnating a catalytically active substance only on pores of a catalyst carrier surface formed of spherical or cylinder shaped particles or in a region close to the external surface using a repulsive force between a hydrophobic solvent and a hydrophilic solvent Specific examples and comparative examples described below will be described in detail.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative, Various modifications are possible, and such modifications are also within the scope of protection of the present invention.

1 is a flowchart schematically illustrating each step of a method of selectively carrying or impregnating a catalytically active substance using a repulsive force between a hydrophilic solvent and a hydrophobic solvent of the present invention.

First, various kinds of porous inorganic oxides having a spherical or cylindrical shape are prepared as catalyst carriers. The porous inorganic oxide catalyst carrier used in the present invention may have at least one or more of silica, alumina, titania, zirconia, and ceria formed on its surface and / or inside thereof with micropores. But is preferably spherical or cylindrical in shape.

After preparing such a porous catalyst support (S10), a first immersion step (SlOO) is performed in which the porous catalyst support particles prepared in the hydrophobic first solvent are sufficiently wetted. At this time, it is preferable that sonication is performed concurrently so that the hydrophobic first solvent can be introduced into the interior of the porous catalyst carrier particles.

As the hydrophobic first solvent, an alcohol having 3 to 6 carbon atoms is preferable, and specifically, n-propanol, n-butanol, n-pentanol, n-hexanol, ethylene glycol, propylene glycol and their derivatives and isomers And more preferably at least one selected from the group consisting of

After the first hydrophobic solvent is sufficiently introduced into the inner pores of the catalyst carrier particles, the first drying step (S200) is carried out using appropriate drying conditions so as to remain only in a specific region within the hydrophobic first solvent particle. At this time, the drying temperature in the first drying step is preferably 50 ° C lower or 50 ° C higher than the boiling point of the hydrophobic first solvent, and the drying time is preferably 1 minute to 120 minutes. However, the amount of the hydrophobic first solvent remaining in the pores of the porous catalyst carrier particles through the first drying step may be controlled, or the dryness temperature and time of the first drying step may vary depending on the type of the first hydrophobic hydrophilic solvent used Of course.

For example, the hydrophobic first solvent on the surface of the catalyst carrier and the hydrophobic property of the inner pores of the outer region in the range of 1/5 to 1/2 of the distance from the surface of the catalyst carrier to the center, The first solvent can be removed. Through this first drying step, the hydrophobic first solvent may remain only in the inner pores of the inner region ranging from 4/5 to 1/2 of the distance from the catalyst carrier surface to the center.

(S300) in which the catalyst carrier in which the first hydrophobic first solvent remains only in a specific region of the inner pores of the catalyst support is immersed in the hydrophilic aqueous solution in which the precursor of the catalytically active substance or the catalytically active substance is dissolved in the second hydrophilic solvent, ≪ / RTI >

At this time, since the hydrophilic first solvent filled in the specific region of the porous catalyst carrier is not mixed with the hydrophilic aqueous solution, the hydrophilic solution is filled only in the surface region of the porous catalyst carrier and in the outer pore region near the surface do. In other words, by performing the second immersion step in which the porous catalyst carrier that has undergone the first immersion step and the first drying step is immersed in the hydrophilic aqueous solution, the hydrophobic first solvent The pore region and the surface of the porous catalyst carrier except the region filled with the hydrophilic solution are filled with the hydrophilic solution.

The proton accepting solution used in the second immersing step is a catalyst active material or a precursor of the catalytically active material dissolved in a second hydrophilic solvent. The precursor of the catalytically active material or the catalytically active material used in the present invention is not particularly limited However, it is preferable to use an expensive metal material or a precursor of a metal material which can be dissolved in a hydrophilic solvent, more preferably a metal salt or a metal salt precursor of any one of platinum, ruthenium, rhodium, cobalt, nickel and palladium.

The hydrophilic second solvent used in the hydrophilic aqueous solution is preferably a polar solvent, and it is preferable to use water as a typical polar solvent.

When the hydrophobic first solvent and the hydrophilic aqueous solution remaining in the surface of the porous catalyst support and the inner pores are removed through the second drying step (S400), the porous catalyst support particles having been subjected to the second immersion step are removed, The precursor of the active material remains only in the region where the hydrophilic solution near the surface and the surface of the porous catalyst carrier exist, so that the catalytically active material can be selectively left only on the surface portion of the formed catalyst carrier.

Therefore, it is possible to selectively impregnate or impregnate the catalytically active material only on the surface portion of the catalyst carrier through the known firing or reduction step (S500), which is the next step, and the internal change of the catalyst carrier particles according to this step is schematically This is shown in Fig.

That is, by immersing the hydrophobic solvent and the hydrophilic solvent in succession, the catalytic active material is immersed only in a specific region of the porous catalyst carrier, thereby preventing the unnecessarily expensive catalytic metal or the precursor of the catalytic metal material from being wasted in the production of the catalyst And has the advantage of economically producing catalysts.

When benzene, toluene, hexane, or the like is used as the hydrophobic primary solvent, since the interaction force between the porous catalyst carrier such as alumina or silica and the primary solvent is weak, the activity of the proton When the porous catalyst carrier is immersed in the aqueous solution, the aqueous solution may penetrate into the internal pores of the porous catalyst carrier particles while the hydrophilic solution pushes benzene, toluene, and hexane. Therefore, solvents having weak interaction with porous catalyst carrier particles such as benzene, toluene, hexane and the like are not suitable for selective impregnation of the catalytically active substance of the present invention.

On the other hand, in the case of alcohols (for example, propanol, butanol, pentanol, hexanol, etc.) having alkyl groups of 3 to 6 carbon atoms and ethylene glycol and propylene glycol as polyhydric alcohols, Silica or porous alumina, so that it is fixed inside the pores during the first immersion step and the first drying step, and the catalytic activity or catalytic activity due to the hydrophobic property of the alkyl group By blocking access to the catalyst carrier particle pores of the proton-accepting solution containing the precursor of the material, selective loading or impregnation of the catalytically active material of the present invention becomes possible as shown in FIG.

Therefore, in the case of a catalyst used in a reaction condition having a high space velocity, such as a steam-methane reforming reaction and a water-gas shift reaction (that is, And the inside of the catalyst particles is not used), the catalyst prepared by the method of the present invention may have the same conversion and selectivity as conventional catalysts even though a small amount of the catalyst active material is carried or impregnated. In addition, when using a Fischer-Tropsch reaction and catalyst particles having a size of 1-3 mm while using a catalyst impregnated or impregnated with a catalytically active substance over the whole area of the particle using a general impregnation method, The production rate and selectivity of hydrocarbons having 5 or more carbon atoms are reduced. However, when the catalyst prepared by the method disclosed in the present invention is used, such a problem can be solved and the efficiency of the Fischer-Tropsch reaction can be increased.

Hereinafter, specific examples of application of the present invention will be described with reference to Comparative Examples and Examples.

The catalyst carrier used in the examples and comparative examples of the present invention is spherical alumina particles. The cross-section of the porous catalyst carrier particles not supported or impregnated in the aqueous solution of the catalyst active particles, as shown in the comparative example of FIG. 3 (a) .

In the embodiment of the present invention, the catalyst active material can be immersed only in a specific region such as the surface region of the porous catalyst carrier through the following experimental procedure. First, the first immersion step is carried out by immersing the porous alumina carrier, which is the catalyst carrier particles, in the hydrophobic first solvent until bubbles do not occur. The first immersion step may be appropriately controlled in consideration of the pore size and porosity of the catalyst carrier, the type and viscosity of the first hydrophobic solvent, the surface tension with the catalyst carrier, and the like. In addition, the hydrophobic first solvent may be sufficiently introduced into the pores of the catalyst carrier by ultrasonication if necessary.

After the first immersion step, the first hydrophobic solvent is removed from the surface of the catalyst carrier by gently shaking the catalyst carrier in a sieve net, the first hydrophobic solvent is put into an oven set at a first drying temperature, and a first drying step .

The drying temperature and time of the first drying step may be appropriately controlled in consideration of the amount of the hydrophilic solution introduced into the pores of the catalyst carrier through the second immersion step, Is preferably selected within the range of 占 0 占 폚, 占 폚, 占 폚, 占 폚, and the drying time is preferably in the range of 1 to 120 minutes.

After the first drying step, a second immersion step is performed in which the catalyst carrier particles are immersed in water as a hydrophilic solvent in a hydrophilic solution containing 0.5 M of cobalt nitrate as a catalytically active substance.

The second immersing step is carried out through the second immersing step, the volume of the void space of the inner pores of the catalyst carrier particles (the space in which the hydrophilic solution containing the catalytically active substance is introduced) produced through the first drying step, The viscosity of the proton-accepting solution, the concentration of the catalytically active substance, and the like, and is preferably selected in the range of 10 to 60 minutes.

The hydrophilic aqueous solution is removed from the surface of the catalyst carrier particles having been subjected to the second immersion step in which they are immersed in the hydrophilic aqueous solution containing the catalytically active substance for a predetermined time.

After the second dipping step, the porous catalyst carrier particles filled with the hydrophobic first solvent at the center portion and the hydrophilic solution containing the catalytically active substance in the vicinity of the surface are subjected to the second drying step, The hydrophobic first solvent filled in the inner pores of the carrier particles and the hydrophilic second solvent of the hydrophilic solution are completely removed.

The temperature and time of the second drying step are not particularly limited and the temperature and time are preferably such that the hydrophobic first solvent and the hydrophilic second solvent are sufficiently removed in the pores of the catalyst carrier particles, Can be set by an ordinary experimenter without any technical difficulty.

Through the second drying step, the catalytically active material remains only in the region of the inner pore region of the catalyst carrier where the hydrophilic solution is filled, and the catalytically active material selectively remains only in the vicinity of the surface of the catalyst carrier through the subsequent firing or reduction step. May be impregnated or impregnated.

3 (b) shows spherical alumina catalyst carrier particles immersed in a 0.5 M aqueous solution of cobalt nitrate, an aqueous solution of catalytically active particles, for 20 minutes and then dried. Through the immersion step for 20 minutes, the whole interior of the catalyst carrier changed to black, which means that the aqueous solution of the catalyst active particle completely penetrated into the interior of the alumina catalyst carrier. When the immersion step is carried out using a 0.5 M aqueous solution of cobalt nitrate, which is a hydrophilic aqueous solution, without using the first hydrophobic solvent, the hydrophilic aqueous solution containing the catalytically active particles is immersed in the interior of the porous catalyst support It was confirmed that it was completely permeated throughout the pores.

Examples and Comparative Examples of the present invention were conducted using the following experimental conditions.

Experimental conditions of Examples 1 to 4 and Comparative Example First drying temperature
[° C] First drying time
[minute] Second immersion time
[minute] Reference drawing Comparative Example - - 20 3 (b) Example 1 130 30 10 3 (c) Example 2 130 120 30 3 (d) Example 3 150 60 30 3 (e) Example 4 150 60 60 3 (f)

(Here, the porous carrier particles are porous alumina, the first hydrophobic solvent is n-pentanol, and the aqueous solution of 0.5 M of cobalt nitrate aqueous solution is used as the hydrophilic solution).

As shown in FIG. 3 (b), when the catalyst is immersed in only the hydrophilic solution as in the comparative example of the present invention, it can be seen that the aqueous solution of cobalt nitrate has penetrated into the entire interior pores up to the central region of the catalyst carrier particle.

In the case of the catalyst prepared under the conditions of Example 1 of the present invention, it can be seen that the cobalt nitrate precursor exists only on the surface portion of the alumina particles as the porous catalyst support as shown in FIG. 3 (c).

In the case of Example 2, the experiment was conducted under conditions in which the drying time of the first drying step was longer than that of Example 1. As shown in FIG. 3 (d), the residual amount of the first hydrophobic solvent is decreased due to the elongated first drying condition, and finally the cobalt nitrate precursor, which is a precursor of the catalytically active substance, As shown in Fig.

This is because as the drying time of the hydrophobic solvent increases, the volume occupied by the hydrophobic solvent decreases inside the particle, thereby reducing the concentricity of the center portion occupied by the hydrophobic solvent, and the reduced vacancy is occupied by the aqueous solution of the cobalt nitrate , And that the amount of the catalytically active substance to be impregnated or impregnated in the porous catalyst carrier can be controlled by controlling the drying conditions.

FIG. 3 (e) and FIG. 3 (f) show the experimental results of Example 3 and Example 4, respectively. The results are obtained by applying the immersion time of the hydrophilic solution to 30 minutes and 60 minutes, respectively. As the second immersion time was increased, it was found that the white concentric circle indicating the position occupied by the hydrophobic solvent was greatly reduced, and the first hydrophobic solvent, pentanol, was largely removed under the first drying condition at 150 ° C., It was confirmed that the cobalt nitrate aqueous solution, which is the precursor of the material, occupied the vacant vacancies.

Through these Comparative Examples and Examples 1 to 4, it was confirmed that the hydrophilic first solvent in the inner pore region of the porous catalyst support was not accessible to the hydrophilic solution in the region occupied by the first immersion step, The volume of the hydrophobic solvent occupied by the pore region inside the porous catalyst carrier was controlled through the control of the first drying condition for removing the first solvent so that the catalytically active material could be selectively supported or impregnated.

Particularly, through the first drying step, the first hydrophobic solvent, which is filled in the outer pores of 1/5 to 1/2 of the distance from the surface of the catalyst carrier to the center of the catalyst carrier, is removed The first hydrophobic solvent is removed from the surface area of the catalyst carrier from the surface of the catalyst carrier by a distance of 4/5 to 1/2 of the distance from the surface of the catalyst carrier through the first drying step It can be experimentally confirmed that the corresponding inner pores can be filled with a hydrophobic solvent.

In order to confirm the controllability and the main factors of the region of the catalytically active substance supported or impregnated in the inner pores of the porous catalyst carrier, the concentration of the catalytically active substance in the hydrophilic first solvent and the concentration of the catalytically active substance in the hydrophilic first solvent are different, , The first drying temperature and the second impregnation time were changed as shown in the following Table 2, and the area where the final catalytically active material was carried or impregnated was directly observed (FIG. 4).

Experimental conditions of Example 5 First drying temperature
[° C] First drying time
[minute] Second immersion time
[minute] Reference drawing Example 5-1 90 5 10 4 (a) Example 5-2 90 10 10 4 (b) Example 5-3 90 One 10 4 (c) Examples 5-4 90 One 5 4 (d) Example 5-5 90 5 5 4 (e) Examples 5-6 90 10 5 4 (f) Examples 5-7 50 5 10 4 (g) Examples 5-9 50 10 10 4 (h)

(Here, the porous carrier particles are porous alumina, the hydrophobic first solvent is n-propanol, and the aqueous solution of cobalt nitrate is used as the hydrophilic solution).

4 (a) to 4 (f), the first drying temperature (90 ° C) and the second immersion time (10 minutes or 5 minutes) were fixed , The penetration depth into the inner pores of the porous catalyst carrier particles of the hydrophilic aqueous solution tended to increase when the first drying time was adjusted to the range of 1 to 10 minutes. It was confirmed that by controlling the drying time of the hydrophobic first solvent, the amount of the catalyst active material supported or impregnated in the vicinity of the surface of the porous catalyst support can be effectively controlled.

Further, it was possible to observe a change in the amount of the catalyst active material carried or impregnated in the vicinity of the surface of the porous catalyst support while changing the first drying temperature while the first drying time was fixed (5 minutes or 10 minutes) ( Examples 5-1 and 5-8 and Examples 5-7 and 5-2). It was confirmed that the hydrophobic first solvent near the surface of the catalyst carrier particles was effectively removed even at a temperature below the boiling point (97 ° C) of the hydrophobic first solvent used. However, when the first hydrophobic solvent was dried at a higher temperature, It can be confirmed that the variation in the thickness of the catalytically active material impregnated is somewhat increased.

Finally, the change of the amount of the catalytically active substance impregnated near the surface of the catalyst carrier was observed while the drying temperature of the first drying condition was fixed (90 DEG C) and the second immersion time was changed (5 minutes, 10 minutes) (Examples 5-4, 5-3: First Drying Time 1 min; Examples 5-5, 5-1: First Drying Time 5 min; Examples 5-6, 5-1: First Drying Time 10 minute).

4 (a) to 4 (f), the change in the second immersion time compared to the change in the first drying temperature and time greatly affects the amount of the catalytically active substance impregnated I could see that it was insane.

As described above, in the present invention, by selectively using a hydrophobic solvent and a hydrophilic solvent, a precursor of the catalytically active substance or the catalytically active substance is positioned near the surface of the porous catalyst carrier, and then the precursor of the catalytically active substance or the catalytically active substance Therefore, it is possible to produce catalytic particles in which the impregnation or impregnation region of the catalytically active substance is finally controlled in the catalyst carrier through the steps of firing / reduction and the like, and the process parameters (the first drying temperature and time, Immersion time), it was possible to selectively fill the inner pore region in the vicinity of the catalyst carrier surface, which corresponds to 1/5 to 1/2 of the distance from the surface of the catalyst carrier particle to the center, with the catalyst active material.

10: catalyst carrier
11: hydrophobic first solvent
13: Chlorophyll solution
14: Catalyst loading or impregnation zone

Claims (13)

(S10) a catalyst carrier preparation step of preparing a spherical or cylindrical porous inorganic oxide as a catalyst carrier;
A first immersion step (S100) of filling the internal pores of the catalyst carrier with a hydrophobic first solvent;
A first drying step (S200) of removing the hydrophobic first solvent in the pores of the area below the surface of the catalyst support through a drying process to thereby leave the hydrophobic first solvent in the pores of the inner central region of the catalyst support;
A second immersion step (S300) of immersing the catalytic active material or the precursor of the catalytic active material in a hydrophilic second solvent to prepare a hydrophilic aqueous solution and then immersing the catalyst carrier having undergone the first drying step in the hydrophilic aqueous solution;
A second drying step (S400) for removing the first solvent remaining in the catalyst carrier and the proton-accepting solution; And
A supporting or impregnating step (S500) of selectively forming the catalytically active substance remaining after the second drying step or the precursor of the catalytically active substance only through the surface of the catalyst carrier and the inner pore region beneath the surface of the catalyst carrier through firing or reduction processes; Lt; / RTI >
The second step of immersing may be performed in a range of 1/5 to 1/2 of the distance from the surface area of the catalyst carrier from which the hydrophobic first solvent has been removed to the center of the catalyst carrier through the first drying step, Lt; RTI ID = 0.0 > a < / RTI > aqueous solution,
Wherein the hydrophilic second solvent is water and the hydrophilic solution is an aqueous solution of a catalytically active substance or an aqueous solution of a precursor of a catalytically active substance,
Wherein the hydrophobic first solvent and the hydrophilic second solvent present in the inner pores of the catalyst carrier are removed through the second drying step, wherein the hydrophobic first solvent and the hydrophilic second solvent are removed through the second drying step. Way The method according to claim 1,
Wherein the porous inorganic oxide is at least one or more selected from the group consisting of silica, alumina, titania, zirconia, and ceria, and a method for supporting a selective surface of a catalytically active material using a repulsive force between a hydrophilic solvent and a hydrophobic solvent
The method according to claim 1,
Wherein the first immersion step comprises immersing the catalyst carrier in the hydrophobic first solvent so that the surface and the inner pores are filled with the hydrophobic first solvent. Surface bearing method
The method according to claim 1,
The drying temperature in the first drying step is selected from the range of 50 ° C lower to 50 ° C higher than the boiling point of the hydrophobic first solvent and the drying time is selected in the range of 1 minute to 120 minutes A method for supporting a selective surface of a catalytically active substance using a repulsive force between a hydrophilic solvent and a hydrophobic solvent
The method according to claim 1,
Wherein the first drying step removes the first hydrophobic solvent which is filled in the outer pores of the first hydrophobic solvent on the surface of the catalyst carrier and the outer pores of the range of 1/5 to 1/2 of the distance from the surface of the catalyst carrier to the center Of selectively supporting a catalytically active substance using a repulsive force between a hydrophilic solvent and a hydrophobic solvent
The method according to claim 1,
Wherein the precursor of the catalytically active substance or the catalytically active substance is a metal salt or a metal salt precursor of any one of platinum, ruthenium, rhodium, cobalt, nickel, and palladium, and a catalytically active substance using a repulsive force between the hydrophilic solvent and the hydrophobic solvent. Of selective surface carrying method
delete The method according to claim 1,
Wherein the hydrophobic first solvent is at least one selected from the group consisting of n-propanol, n-butanol, n-pentanol, n-hexanol, ethylene glycol, propylene glycol, and derivatives and isomers thereof. Of selectively supporting a catalytically active substance using a repulsive force between a hydrophobic solvent and a hydrophobic solvent
delete delete The method according to claim 1,
Wherein the immersing time in the second immersing step is in the range of 1 minute to 60 minutes. The method for supporting a selective surface of a catalytically active substance using a repulsive force between a hydrophilic solvent and a hydrophobic solvent
The method according to claim 1,
In the first immersion step, sonication is performed so that the hydrophobic first solvent can fill in the inner pores of the catalyst carrier particles. The hydrophobic solvent may be selected from the group consisting of Surface bearing method
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