KR101578071B1 - Preparation method of high dispered novel metal catalyst - Google Patents

Preparation method of high dispered novel metal catalyst Download PDF

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KR101578071B1
KR101578071B1 KR1020150070434A KR20150070434A KR101578071B1 KR 101578071 B1 KR101578071 B1 KR 101578071B1 KR 1020150070434 A KR1020150070434 A KR 1020150070434A KR 20150070434 A KR20150070434 A KR 20150070434A KR 101578071 B1 KR101578071 B1 KR 101578071B1
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noble metal
catalyst
acid
supported
solution
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이만식
김지선
백재호
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주식회사 디알액시온
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/02—Solids
    • B01J35/023—Catalysts characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing

Abstract

The present invention relates to a process for producing a noble metal-supported catalyst, and more particularly, to a process for preparing a high-dispersion noble metal-supported catalyst by introducing a highly efficient dispersion process of a carrier using a high shear reactor. The method for preparing a noble metal-supported catalyst according to the present invention is carried out in a high-shear reactor. Unlike the ultrasonic method or the impeller method, a stirring method in a general reactor is a method in which noble metal particles having a size of about 2 to 5 nm A catalyst having a high catalytic activity can be produced because the catalyst has a large size distribution and a high degree of dispersion of the noble metal. In addition, since the dispersion step of dispersing the carrier is removed, mass production is easy, so that it can be usefully used in place of the conventional method for producing a noble metal supported catalyst.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a high-

More particularly, the present invention relates to a method for preparing a noble metal supported catalyst by introducing a highly efficient dispersion process of a carrier using a high shear reactor.

Precious metal supported catalysts are widely used for selective hydrogenation of unsaturated organic compounds. In particular, palladium / carbon catalysts are useful for the purification of crude terephthalic acid, wherein some impurities in the crude terephthalic acid, such as 4-carboxybenzaldehyde (4-CBA), are converted to other compounds via hydrogenation and then the terephthalic acid product Can be isolated through crystallization.

In addition, as the chlorofluorocarbons (CFC) compounds have been found to be the main causes of ozone depletion and global warming, the development of CFC substitute materials has become an important research task, and the hydrogenation reaction of CFC using the precious metal- Research.

Since the noble metal supported catalyst typically contains a single active component, studies known in the prior art for the improvement of such catalysts have focused primarily on the structure of the support and the distribution of the noble metal on the support, It actually has a great influence on the properties of the catalyst.

Since the hydrogenation purification reaction of terephthalic acid is a first-order reaction and the reaction rate is fast, it is difficult for the reactants to diffuse into the catalyst particles during the reaction, and thus the active components in the catalyst particles can not function well. Therefore, in order to fully use the noble metal, the catalyst is generally prepared as an egg shell type in which the active component, that is, the noble metal is mainly supported on the surface of the support.

Since the hydrogenation reaction is generally performed on the surface of the noble metal in the case of the catalyst having the same noble metal loading amount, the larger the degree of dispersion of the noble metal in the catalyst and / or the higher the content of the noble metal crystallite supported in the catalyst and / The better the thermal stability of the catalyst, the higher the activity of the catalyst and the longer service life of the catalyst.

However, when a solution containing a noble metal compound (such as sodium chloropalladate or palladium chloride) is directly loaded onto the activated carbon, a very thin glossy layer of noble metal will appear rapidly on the surface of the activated carbon. The reason for this is mainly that the surface of the activated carbon has a reducing group, for example, an aldehyde group and free electrons, which easily reduce noble metal ions to noble metals. As a result, the catalyst prepared as described above has a very low dispersion degree of noble metal.

One approach to overcome this problem is to convert the noble metal ions in the impregnating liquid containing the noble metal compound into the insoluble compound before impregnation. For example, a water-soluble noble metal compound can be hydrolyzed to insoluble Pd (OH) 2 or PdO.H 2 O at room temperature, which is then supported on activated carbon, followed by a reducing agent such as formaldehyde, sodium formate, glucose , Formic acid or hydrogen gas. In this way, movement of the noble metal and growth of the crystallite can be prevented. For example, USP 3,138,560 teaches that hydrogen peroxide is added to the impregnation solution to hydrolyze the water soluble Pd compound into an insoluble compound followed by impregnation. USP 4,476,242 discloses the preparation of a Pd compound-containing impregnation solution by using an organic solvent such as methanol, pyridine, or the like. It is also said to be very effective in preventing Pd migration and larger palladium crystallites.

Also, there are patents reporting that the precious metal precursor solution is converted to a noble metal-containing colloid solution by adjusting the pH value, which can prevent reduction groups on the activated carbon surface from directly reducing noble metal ions to zero-valent noble metals.

Thus, in the conventional method for preparing a noble metal-supported catalyst, the noble metal precursor solution is reacted with a stabilizer (trisodium citrate) to prepare a noble metal precursor solution, the pH is neutralized with a precipitant solution (NaOH) (Or activated carbon) was added to the carbon surface, followed by a reduction process in which a reducing agent (sodium borohydride) was added to reduce the noble metal on the surface of the carbon.

At this time, since the lowering of the dispersion of the carbon carrier with respect to the solvent affects the overall dispersion, a sufficient dispersion step is required before the carrier is charged. However, for the preparation of the transition metal catalyst, the step of dispersing carbon is an important step in determining the degree of dispersion of the transition metal, but it takes a long time for this step because of the low dispersibility of the carbon in the solvent. Takeshi Kubota et al., In the literature, the dispersion time of the carbon carrier in the preparation of the noble metal supported catalyst proceeds for a maximum of 20 hours, and this step affects the productivity of the catalyst.

Therefore, it is required to develop a method for producing a palladium / carbon catalyst which is still easy to manufacture and which has a high degree of dispersion of palladium and high catalytic activity.

The present inventors have made efforts to produce an improved noble metal supported catalyst in consideration of this point. As a result, it has been found that when a noble metal supported catalyst is produced in a high shear reactor, A noble metal-supported catalyst having a higher degree of dispersion than a catalyst is produced, thereby reducing the overall process time and increasing the catalytic activity. Thereby completing the manufacturing method.

Accordingly, it is an object of the present invention to provide a method for producing a transition metal nanoparticle having a narrow particle size distribution by a simple process.

In order to solve the above problems, it is an object of the present invention to provide a method for producing a high dispersion of a noble metal supported catalyst using a high shear reactor.

Another object of the present invention is to provide a highly dispersed noble metal-supported catalyst produced by the above-mentioned production method.

In order to solve the above problems, the present invention provides, as one aspect,

(a) a first step of pretreating carbon black with an inorganic acid;

(b) a second step of preparing a precious metal precursor solution; And

(c) A noble metal precursor solution is agitated in a high-shear reactor, the pH is adjusted to neutrality by using a precipitant solution, and then impregnated with pretreated carbon black to prepare a noble metal-supported carbon catalyst on the surface of the carbon black. Wherein the catalyst is supported on the catalyst support.

Preferably, the first step is characterized in that the carbon black is pretreated by treating the carbon black with an inorganic acid, then washing it with water until it becomes neutral, and then drying the washed carbon black.

Also preferably, the inorganic acid is at least one acid selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; The inorganic acid has an acid concentration of 0.01 to 5.0 M; The acid treatment time is in the range of 0.5 to 8 hours; The drying is performed at a temperature of 60 to 150 DEG C for 0.5 to 10 hours.

Preferably, the second step is a step of reacting a solution obtained by dissolving a noble metal salt compound in an inorganic acid with a stabilizer to prepare a precious metal precursor solution.

Preferably, the noble metal is at least one selected from the group consisting of palladium, platinum, ruthenium, and rhodium.

Also preferably, the stabilizer is selected from the group consisting of trisodium citrate, sodium gluconate and sodium tartrate.

Preferably, the noble metal salt is dissolved at a concentration of 0.01 to 5.0 M based on the inorganic acid having an acid concentration of 0.01 to 5.0 M, and the stabilizer is added in an amount of 1 to 40 parts by weight based on the dissolved noble metal salt solution .

Preferably, in the third step, the pH of the palladium precursor solution is adjusted to neutrality using the precipitant solution while stirring in a high-shear reactor, and then impregnated with the pretreated carbon black, Lt; 0 > C for a period of time.

Also preferably, the precipitant solution is characterized in that it is selected from the group consisting of NaOH, KOH, NaHCO 3 and Na 2 CO 3 .

The noble metal-containing metal supported catalyst can be obtained by reducing the catalyst precursor thus produced.

The reducing agent used in the reduction is not particularly limited, and examples thereof include hydrazine, formaldehyde, sodium borohydride, hydrogen, formic acid, salts of formic acid, ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-heptene, 2-heptene, 1-hexene, 2-hexene, cyclohexene, allyl alcohol, methallyl alcohol, 1,2-ethanediol, acrolein and methacrolein. Among these, hydrogen, hydrazine, formaldehyde, formic acid, salts of formic acid, 1,2-ethanediol, sodium borohydride and the like are preferable. These may be used in combination of two or more.

According to another aspect of the present invention,

(a) a first step of pretreating carbon black with an inorganic acid;

(b) a second step of preparing a precious metal precursor solution; And

(c) A noble metal precursor solution is agitated in a high-shear reactor, the pH is adjusted to neutrality by using a precipitant solution, and then impregnated with pretreated carbon black to prepare a noble metal-supported carbon catalyst on the surface of the carbon black. And a high-dispersion noble metal-supported catalyst prepared by a method comprising the steps of:

Preferably, the noble metal-supported catalyst has a uniform particle size distribution of noble metal particles of 2 to 5 nm and a noble metal dispersion of 20 to 40%.

As described above, the process for preparing a noble metal-supported catalyst according to the present invention is carried out in a high-shear reactor, and thus, unlike an ultrasonic or impeller-assisted stirring method in a general reactor, The catalyst having a uniform particle size distribution of 2 to 5 nm and a high degree of dispersion of the noble metal can be produced and a catalyst having a high catalytic activity can be produced and the dispersion process for dispersing the carrier is excluded and the process is simplified by introducing a high- It can be usefully used instead of the conventional method for producing a noble metal supported catalyst.

According to the method for producing a noble metal-supported catalyst according to the present invention, nanoparticles having a narrow particle size can be produced by a simple process. Such noble metal-supported catalysts are useful for fine chemical processes, automobile exhaust gas catalysts, Applicable

1 is a schematic view showing a process for producing a noble metal-supported catalyst according to an embodiment of the present invention.
2 is an XRD analysis graph of a palladium-supported carbon catalyst prepared according to one embodiment of the present invention and one comparative example.
3 is an FE-TEM image of a palladium-supported carbon catalyst prepared according to one embodiment of the present invention and one comparative example.

Hereinafter, the present invention will be described in detail.

Dispersed carbon catalyst supporting a noble metal by rapidly dispersing a carbon carrier in a precursor solution in a short time so that a highly dispersed catalyst can be produced in a short period of time without going through a separate carbon dispersion step, The present invention relates to a method for producing a high dispersion noble metal supported catalyst having a narrow particle size distribution and a high dispersion degree without a process and a heating process.

Specifically, a method for producing a high dispersion of a noble metal-supported catalyst according to the present invention comprises:

(a) a first step of pretreating carbon black with an inorganic acid;

(b) a second step of preparing a precious metal precursor solution; And

(c) A noble metal precursor solution is agitated in a high-shear reactor, the pH is adjusted to neutrality by using a precipitant solution, and then impregnated with pretreated carbon black to prepare a noble metal-supported carbon catalyst on the surface of the carbon black. Step.

First, the first step is a step of pretreating carbon black with an inorganic acid.

The pretreatment step is carried out to form a functional group on the surface of the carbon carrier, change the pore distribution, and remove impurities, and a method commonly used in the art can be used. In one example, the pretreatment can be carried out by treating the carbon black with inorganic acid, then washing with water until neutral, and then drying the washed carbon black.

The inorganic acid may be at least one acid selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and the inorganic acid may have an acid concentration of 0.01 to 5.0 M But it is not limited thereto.

The acid treatment may be carried out for 0.5 to 8 hours, and the drying may be carried out at a temperature of 60 to 150 ° C for 0.5 to 10 hours.

Next, the second step is a step of preparing a precious metal precursor solution.

The noble metal precursor solution can be prepared by reacting a solution prepared by dissolving a noble metal salt compound in an inorganic acid with a stabilizer.

At this time, the noble metal is preferably, but not limited to, at least one selected from the group consisting of palladium, platinum, ruthenium, and rhodium. The noble metal salt is preferably a basic metal salt of the noble metal, such as a nitrate salt, an acetate salt, a sulfate salt, a hydrochloride salt or the like.

The inorganic acid may be selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, preferably hydrochloric acid.

Further, the stabilizer may be selected from the group consisting of trisodium citrate, sodium gluconate and sodium tartrate.

The noble metal salt may be dissolved in a concentration of 0.01 to 5.0 M with respect to an inorganic acid having an acid concentration of 0.01 to 5.0 M, and the stabilizer is preferably added in an amount of 1 to 40 parts by weight based on the dissolved noble metal salt solution .

Next, the third step is a step of impregnating the noble metal precursor solution with carbon black pretreated to prepare a noble metal-supported carbon catalyst carrying a noble metal on the surface of the carbon black.

At this time, the above step is preferably carried out in a high shear reactor. The high-shear reactor is a device that uniformly mixes two materials by rotating at high speed. Through the strong rotation of the rotor of the inner impeller, the target material is sucked through the fine gaps between the impellers and the rotor, finely dispersed by the high-speed rotary blade, and mixed between the two materials.

Specifically, in the above step, the pH of the precious metal precursor solution is adjusted to neutrality using the precipitant solution while stirring in a high-shear reactor, and then the pretreated carbon black is calculated by taking into consideration the content of the noble metal in the catalyst to be produced Followed by stirring at -5 to < RTI ID = 0.0 > 25 C < / RTI > for 0.5 to 5 hours. At this time, the carbon black as the support is characterized in that carbon black pretreated without being subjected to a separate dispersion process can be injected.

At this time, the precipitant solution may be selected from the group consisting of NaOH, KOH, NaHCO 3 and Na 2 CO 3 , but is not limited thereto.

The reducing agent used for the reduction is not particularly limited, and for example, hydrazine, formaldehyde, sodium borohydride, hydrogen, formic acid, and salts of formic acid are preferable. These may be used in combination of two or more.

In addition, the present invention provides a noble metal-supported catalyst produced by the above production method.

The noble metal catalyst is characterized in that it is produced by a production method using a high-shear reactor according to the present invention. The common description of both inventions is omitted in order to avoid excessive complexity of the specification according to the repetitive description.

The noble metal catalyst thus prepared exhibits a uniform particle size distribution of noble metal particles of 2 to 5 nm and a dispersion degree of noble metal of 20 to 40% (See Fig. 3 and Table 1).

Hereinafter, the present invention will be described in detail with reference to examples, but these examples should not be construed as limiting the scope of the present invention.

<Examples> Preparation of palladium-supported carbon catalyst using a high-shear reactor

Step 1: Carbon black pretreatment

(Vol% 1: 1) using 2M H 2 SO 4 and 2M HNO 3 for the formation of functional groups, changes in pore distribution and removal of impurities on the surface of a carbon carrier (Black pearl 2000, Cabot) &Lt; / RTI &gt; The agitated carbon black suspension was filtered using a vacuum filtration filter, and the filtrate was washed several times with distilled water until the pH became neutral, followed by drying at 80 ° C for 5 hours.

Step 2: Preparation of palladium precursor solution

Next, to prepare a palladium (Pd) precursor solution, a solution of H 2 PdCl 4 was prepared by dissolving PdCl 2 to 0.1 M in an aqueous HCl solution. Thereafter, an aqueous solution of 100 mL 2 mM sodium gluconate (C 6 H 11 NaO 7 ) was added and dissolved to prepare a palladium precursor solution.

Step 3: Preparation of palladium-supported carbon catalyst

The Pd precursor solution was stirred in a high shear reactor and neutralized by the addition of 0.1 M aqueous sodium hydroxide (NaOH) solution. Then, the carbon black pretreated with the Pd precursor solution was added so that the weight ratio of Pd was 5%, and then the mixture was stirred at 10 ° C for 2 hours. Then, 0.5M sodium borohydride (NaBH 4 ) aqueous solution was added, and the mixture was sufficiently stirred. The prepared palladium / carbon catalyst was washed several times with distilled water after filtration, and vacuum dried at 80 ° C for 5 hours.

Example 2: Preparation of rhodium supported carbon catalyst using a high shear reactor

In order to prepare a rhodium (Rh) precursor solution in the second step, RhCl 2 was dissolved in an aqueous solution of HCl so that the concentration of RhCl 2 became 0.1 M, and a solution of H 2 RhCl 4 was added thereto . Then, an aqueous solution of 100 mL 2 mM sodium gluconate (C 6 H 11 NaO 7 ) was added and dissolved to prepare a rhodium precursor solution. In the third step, rhodium was used as a noble metal precursor solution.

&Lt; Example 3 > Preparation of platinum-supported carbon catalyst using a high shear reactor

The first step and the second step are carried out in the same manner as the example, except that the first step and the second step are carried out in the same manner as in the examples, In the second step, H 2 PtCl 4 solution was prepared by dissolving PtCl 2 to 0.1 M in an aqueous HCl solution to prepare a platinum (Pt) precursor solution. Then, 100 mL of 2 mM sodium gluconate (C 6 H 11 NaO 7 ) aqueous solution was added and dissolved to prepare a platinum precursor solution. In the third step, platinum was used as a precursor solution of the noble metal.

&Lt; Comparative Example 1 > Preparation of palladium-supported carbon catalyst according to the conventional method

The first step and the second step were carried out in the same manner as in the examples.

In the third step, the palladium precursor solution was neutralized by adding 0.1 M sodium hydroxide (NaOH) solution while ultrasonically stirring in a general reactor. Thereafter, carbon black pretreated with the palladium precursor solution was added so that the weight ratio of Pd was 5%, and the mixture was stirred at 10 캜 for 2 hours. After stirring for 2 hours, a 0.5M aqueous solution of sodium hydrobromide (NaBH 4 ) was added as a reducing agent to reduce Pd on the surface of the carbon, and the mixture was sufficiently stirred. The prepared palladium / carbon catalyst was washed several times with distilled water after filtration, and vacuum dried at 80 ° C for 5 hours.

&Lt; Comparative Example 2 > Preparation of palladium-supported carbon catalyst according to the conventional method

A palladium / carbon catalyst was prepared in the same manner as in Comparative Example 1, except that impeller stirring was used as a stirring method.

&Lt; Comparative Example 3 > Preparation of rhodium-supported carbon catalyst according to the conventional method

A rhodium / carbon catalyst was prepared in the same manner as in Example 2 except that impeller stirring was used as a stirring method.

&Lt; Comparative Example 4 > Preparation of platinum-supported carbon catalyst according to the conventional method

A platinum / carbon catalyst was prepared in the same manner as in Example 3, except that impeller stirring was used as a stirring method.

Experimental Example 1 X-ray diffraction analysis (XRD)

The results of XRD analysis of the palladium-supported carbon catalyst prepared in Example 1 and Comparative Examples 1 and 2 of the present invention are shown in FIG.

As shown in FIG. 2, all of the catalysts prepared from the XRD analysis were able to confirm the graphite peaks at 2? = 25 占 and were found to have (1 1 1), (2 0 0) at 2? = 39.9, 46.4 and 67.8 占) And the (Pd) characteristic peak of (2 2 0) plane.

In addition, the Pd peak was low, indicating that Pd was well supported on the carbon surface, and that there was no peak of the Pd peak, and no conversion to Pd was observed.

<Experimental Example 2> Field-emission scanning electron microscope (FE-TEM) analysis

The FE-TEM analysis results of the palladium-supported carbon catalysts prepared in Example 1 and Comparative Examples 1 to 3 of the present invention are shown in FIG.

3 (a) is a Pd-supported carbon catalyst prepared according to Example 1 of the present invention, and (b) to (c) is an FE-TEM image of the palladium-supported carbon catalyst prepared in Comparative Example 1-2 .

As shown in FIG. 3, the palladium-supported carbon catalyst prepared using the high-shear reactor according to the present invention has a uniform particle size distribution of about 2 to 5 nm and has a high degree of dispersion (see (a) ). In the case of catalytic synthesis using ultrasonic agitation, the Pd particle size was widely distributed in the range of 2 to 25 nm, though the particle size was not uniform (see (b)). This is thought to be a result of the stability of the colloid being reduced due to the long term ultrasonic dispersion. In addition, the preparation of the catalyst using the impeller agitator has a uniform particle size distribution of 2 to 10 nm, but it has been confirmed that the aggregation of Pd is partially observed to have a low dispersion degree (see (c)).

Thus, the palladium-supported carbon catalyst using the high-shear reactor according to the present invention can produce a palladium-supported carbon having a uniform particle size distribution of palladium particles of 2 to 5 nm on the surface of the carbon support, A catalyst can be produced.

&Lt; Experimental Example 3 > Palladium-supported carbon catalyst activity measurement

The activity of palladium / carbon catalyst was confirmed by adsorption amount of CO gas of Pd particles. The amount of Pd was calculated by using this amount and the catalytic activity was compared. The adsorption amount of CO on Pd was measured by pulse technique at 50 ° C, and Pd was assumed to adsorb 1: 2 with CO.

Then, the degree of dispersion of palladium dispersed in carbon was calculated using the following equation (1) using the CO gas adsorption amount.

Figure 112015048439884-pat00001

Where M is the molecular weight of Pd, and c is the loading amount (wt%) of the metal on the carbon surface. In this case, V chem is the amount of adsorbed CO gas (mmol / g), SF is the adsorption constant of CO gas to Pd, to be.

Table 1 shows the amounts of adsorbed CO gas and the dispersions of Pd in the palladium / carbon catalyst prepared in Examples of the present invention and Comparative Example 1-3, which were calculated through the above formula.

division Stirring method CO gas adsorption amount
(mmol / g) Dispersion degree of Pd
(%) Example 1 High share stirring 0.0609 27.8 Comparative Example 1 Ultrasonic agitation 0.0479 20.4 Comparative Example 2 Impeller stirring 0.0266 11.3

As shown in Table 1, when the high-shear stirring method was employed in the high-shear reactor according to the present invention, the adsorption amount of CO gas was 0.0609 mmol / g in the preparation of palladium-supported carbon catalyst using high shear, 0.0479 mmol / g) or the impeller stirring (0.0266 mmol / g).

<Experimental Example 4> Measurement of activity of rhodium-supported carbon catalyst and platinum-supported carbon catalyst

The activity and the dispersity of the rhodium-supported carbon catalyst and the platinum-supported carbon catalyst were measured in the same manner as in Experimental Example 3, and the results are shown in Table 2.

division Precious metal Stirring method CO gas adsorption amount
(mmol / g) Dispersion degree of Pd
(%) Example 2 rhodium High share stirring 0.0554 25.3 Comparative Example 3 Impeller stirring 0.0234 10.7 Example 3 platinum High share stirring 0.0527 24.1 Comparative Example 4 Impeller stirring 0.0203 9.3

As shown in Table 2, when the high-shear stirring method was employed in the high-shear reactor according to the present invention, the adsorption amount of CO gas was 0.0554 mmol / g in the preparation of rhodium / carbon catalyst using high shear, (0.0234 mmol / g and 0.0203 mmol / g, respectively), indicating that the catalyst activity was increased by at most 2.25 times and 2.5 times higher than that of using impeller agitation (0.0234 mmol / g and 0.0203 mmol / g respectively).

As described above, the method for preparing a noble metal-supported catalyst according to the present invention is carried out in a high-shear reactor, whereby a high degree of dispersion can be expected in the production of a noble metal-supported catalyst without the step of dispersing the carrier, Since the process is simple and mass production is easy, it can be usefully used instead of the conventional method for producing a noble metal-supported carbon catalyst. .

The present invention has been described with reference to the preferred embodiments. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the disclosed embodiments should be considered in an illustrative rather than a restrictive sense. The scope of the present invention is defined by the appended claims rather than by the foregoing description, and all differences within the scope of equivalents thereof should be construed as being included in the present invention.

Claims (11)

(a) a first step of pretreating carbon black by treating the carbon black with inorganic acid, then washing with water until it becomes neutral, and then drying the washed carbon black;
(b) a second step of reacting a solution prepared by dissolving a noble metal salt compound in an aqueous inorganic acid solution with a stabilizer to prepare a noble metal precursor solution; And
(c) adjusting the pH of the noble metal precursor solution to neutrality using the precipitant solution while stirring in a high-shear reactor, then impregnating the pretreated carbon black, and stirring the mixture at -5 to 25 ° C for 0.5 to 5 hours, And a third step of preparing a carbon catalyst having a noble metal supported thereon,
Wherein the stabilizer is selected from the group consisting of trisodium citrate, sodium gluconate and sodium tartrate,
Wherein the noble metal supported catalyst has a uniform particle size distribution of noble metal particles of 2 to 5 nm and a dispersion degree of noble metal of 20 to 40%
(JP) METHOD FOR PREPARING HIGH DISPERSION OF CATALYST SUPPORTED TO PRE - METAL The method according to claim 1,
The inorganic acid is at least one acid selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; The inorganic acid has an acid concentration of 0.01 to 5.0 M; The acid treatment time is in the range of 0.5 to 8 hours; Wherein the drying is performed at a temperature of 60 to 150 DEG C for 0.5 to 10 hours. The method according to claim 1,
Wherein the noble metal is at least one selected from the group consisting of palladium, platinum, ruthenium and rubidium. The method according to claim 1,
In the second step, the noble metal salt is dissolved at a concentration of 0.01 to 5.0 M with respect to an inorganic acid having an acid concentration of 0.01 to 5.0 M, and the stabilizer is added in an amount of 1 to 40 parts by weight based on the dissolved noble metal salt solution Wherein the noble metal supported catalyst is supported on a support. The method according to claim 1,
Wherein the precipitant solution is selected from the group consisting of NaOH, KOH, NaHCO 3 and Na 2 CO 3 . A noble metal-supported catalyst produced by the production method according to any one of claims 1 to 5, wherein the noble metal-supported catalyst has a uniform particle size distribution of noble metal particles of 2 to 5 nm in size, 20 to 40%. &Lt; RTI ID = 0.0 &gt; 21. &lt; / RTI &gt; delete delete delete delete delete
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