PLATINUM-LOADED ALUMINA CATALYST, METHOD OF PRODUCING SAME, AND METHOD OF DEHYDROGENATING HYDROGENATED AROMATIC USING THE CATALYST

Abstract

To provide a platinum-loaded alumina catalyst with an improved catalyst life.

A platinum-loaded alumina catalyst includes an alumina carrier, and platinum loaded on the alumina carrier, wherein the alumina carrier includes a γ-alumina carrier having a surface area of 200 m.sup.2/g or more, a pore volume of 0.50 m.sup.2/g or more, an average pore diameter in a range of 60 to 150 Å, with pores having a pore diameter in a range of ±30 Å from the average pore diameter occupying 60% or more of a total pore volume, platinum particles are loaded on γ-alumina carrier in a range of 0.1 to 1.5% by weight calculated as elemental platinum (Pt), and 70% or more of the platinum particles have a size of 8 to 15 Å by direct observation using a transmission electron microscope.

Claims

1. A platinum-loaded alumina catalyst, comprising: an alumina carrier; and platinum loaded on the alumina carrier, wherein the alumina carrier comprises a γ-alumina carrier that has a surface area of 200 m.sup.2/g or more, a pore volume of 0.50 cm.sup.3/g or more, and an average pore diameter in a range of 60 to 150 Å, with pores having a pore diameter in a range of ±30 Å from the average pore diameter occupying 60% or more of a total pore volume, particles of the platinum are loaded on the γ-alumina carrier in a range of 0.1 to 1.5% by weight calculated as elemental platinum (Pt), and 70% or more of the particles of the platinum have a size of 8 to 15 Å by direct observation using a transmission electron microscope.

2. The platinum-loaded alumina catalyst according to claim 1, wherein the γ-alumina carrier contains sulfur or a sulfur compound in a range of 0.5 to 1.2% by weight calculated as elemental sulfur (S).

3. The platinum-loaded alumina catalyst according to claim 1 or 2, wherein the γ-alumina carrier has alkali metals loaded thereon in a range of 0.5 to 1.5% by weight, and the alkali metals are sodium and potassium.

4. A method of producing the platinum-loaded alumina catalyst according to claim 1, wherein in a preparation of the γ-alumina carrier, an alkaline aqueous solution is added to an acidic aqueous solution containing aluminum, and a boehmite obtained as aluminum hydroxide is dried and thereafter is calcined at a temperature in a range of 250 to 400° C. for a time period in a range of 1 to 12 hours.

5. The method of producing the platinum-loaded alumina catalyst according to claim 4, wherein, by using a chloroplatinic acid aqueous solution as a platinum reagent aqueous solution, the γ-alumina carrier after the calcination is impregnated with the platinum such that a content thereof is in a range of 0.5 to 1.5% by weight calculated as elemental platinum, and a resultant is dried and thereafter is calcined at a temperature in a range of 250 to 400° C.

6. The method of producing the platinum-loaded alumina catalyst according to claim 5, wherein the γ-alumina carrier that has been impregnated with the platinum, dried, and thereafter calcined is subjected to hydrogen reduction, and a temperature of the hydrogen reduction is higher than the temperature for calcining the boehmite after drying, is higher than the temperature for calcining the γ-alumina carrier impregnated with the platinum and dried, and is in a range of 300 to 450° C.

7. The method of producing the platinum-loaded alumina catalyst according to claim 6, wherein a time period of the hydrogen reduction is in a range of 1 to 15 hours.

8. The method of producing the platinum-loaded alumina catalyst according to claim 4, wherein the γ-alumina carrier contains sulfur or a sulfur compound in a range of 0.5 to 1.2% by weight calculated as elemental sulfur (S).

9. The method of producing the platinum-loaded alumina catalyst according to claim 4, wherein the γ-alumina carrier after the calcination is impregnated with ammonium sulfate aqueous solution and thereafter is calcined at a temperature in a range of 250 to 400° C. for a time period in range of 1 to 12 hours.

10. The method of producing the platinum-loaded alumina catalyst according to claim 5, wherein the γ-alumina carrier containing no sulfur or the γ-alumina carrier containing sulfur is impregnated with platinum, is dried, and thereafter is calcined to generate a platinum-loaded γ-alumina carrier, the platinum-loaded γ-alumina carrier is impregnated with alkali metals such that the alkali metals are contained in a range of 0.5 to 1.5% by weight, is dried, and thereafter is subjected to hydrogen reduction without being calcined, and a temperature of the hydrogen reduction is higher than the temperature for calcining the boehmite after drying, is higher than the temperature for calcining the γ-alumina carrier impregnated with the platinum and dried, and is in a range of 300 to 450° C.

11. The method of producing the platinum-loaded alumina catalyst according to claim 10, wherein the alkali metals are sodium and potassium.

12. The method of producing the platinum-loaded alumina catalyst according to claim 10, wherein a time period of the hydrogen reduction is in a range of 1 to 15 hours.

13. A method of dehydrogenating a hydrogenated aromatic, comprising dehydrogenating a hydrogenated aromatic by using the platinum-loaded alumina catalyst according to claim 1.

14. The method of dehydrogenating a hydrogenated aromatic according to claim 13, wherein the hydrogenated aromatic is one member or a mixture of two or more members selected from the group consisting of a hydride of monocyclic aromatic, a hydride of bicyclic aromatic, and a hydride of compound having 3 or more aromatic rings.

15. The method of dehydrogenating a hydrogenated aromatic according to claim 13, wherein the hydrogenated aromatic is one member or a mixture of two or more members selected from the group consisting of methylcyclohexane, cyclohexane, trimethylcyclohexane, decalin, and dibenzotriol.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0058] FIG. 1 is an explanatory diagram showing (A) a transmission electron micrograph in 2000s and (B) a transmission electron micrograph in recent years of a catalyst;

[0059] FIG. 2 is an explanatory diagram of (A) an egg shell-type metal-loaded catalyst and (B) a uniform-type metal-loaded catalyst; and

[0060] FIG. 3 is an explanatory diagram related to measurement of platinum particle diameters based on the transmission electron micrograph.

MODE(S) FOR CARRYING OUT THE INVENTION

[0061] FIG. 1 shows photographs of catalyst taken by (A) a transmission electron microscope in 2000s and (B) a transmission electron microscope in recent years. FIG. 1(A) is a photograph of an egg shell-type catalyst disclosed in Patent Document 1 (JP4652695B2). The photograph of FIG. 1(A) was taken at 1.8 million times magnification by using HITACHI, HD-200 electron microscope, which was a state-of-the-art transmission electron microscope at the time of 2006. FIG. 1(B) is a photograph of a uniform-type platinum-loaded alumina catalyst disclosed in Patent Document 2 (JP4142733B2). The photograph of FIG. 1(B) was taken at 2 million times magnification by using JEOL, JEM-ARM200 electron microscope in 2018.

[0062] Note that the disclosure of the all documents referred to herein, including JP4652695B2 and JP4142733B2, constitutes a part of the present specification, and detailed description thereof is omitted.

[0063] With the resolution of a general transmission electron microscope in 2000s, it was not possible to measure platinum particle diameters of several nanometers by direct observation, and therefore, it was common at that time to estimate the particle diameters by CO-pulse method (CO pulse adsorption method). Currently, owing to the progress of electron microscope performance, it is possible to directly observe particles of several Å and molecules such as benzene rings with a resolution of about 1 Å.

[0064] In the transmission electron micrograph in 2000s shown in FIG. 1(A), it is seen that multiple platinum particles are each independently loaded but the outline of white dots (namely, platinum particles) is unclear and thus there is a tendency that the particles appear bigger than they actually are.

[0065] In the transmission electron micrograph in recent years shown in FIG. 1(B), it is seen that the outline of white dots (the platinum particles) can be observed more clearly. Therefore, the particle diameters of the platinum loaded on the alumina carrier can be measured with higher accuracy by direct observation with the transmission electron microscope in recent years. The average particle diameter of the platinum particles in the platinum-loaded alumina catalyst according to the present invention can be obtained by measuring the particle diameters of a predetermined number (typically, about 50) of platinum particles in a photograph taken by the transmission electron microscope as shown in FIG. 1(B) and calculating the average value thereof. In the transmission electron microscope, it is preferred to set the magnification such that the particle diameters of the predetermined number of platinum particles are fit in the photograph (for example, with the platinum-loaded alumina catalyst of the present invention, 40 to 50 platinum particles can be observed in the field of view at 2 million times magnification). The size of each platinum particle can be measured by aligning a measurement line with the outline of the particle on the computer screen equipped in the electron microscope system. At this time, in a case where the shape of the platinum particle has a long-axis diameter and a short-axis diameter, the long-axis diameter can be measured by aligning the measurement line with the outline of the long-axis diameter, and the short-axis diameter can be measured in a similar manner. Since there is substantially no difference between the long-axis diameter and the short-axis diameter for the platinum particles on the platinum-loaded alumina catalyst of the present invention, it is possible to use the long-axis diameter as a representative value. Also, it is also possible to measure the size of the particle diameters by printing the image and measuring the particle diameters with a ruler to compare with a scale on the image.

[0066] In contrast to this, the platinum particle diameters disclosed in the above-described Patent Document 1 and Patent Document 2 are estimated values according to the CO-pulse method. It can be considered that there is an error between the particle diameters estimated by the CO-pulse method and the particle diameters measured by direct observation using the transmission electron microscope. This is because in the CO-pulse method, the particle diameters are likely to be estimated smaller compared to the particle diameters measured by direct observation. In the CO-pulse method, since 1 molecule of CO is adsorbed on 1 atom of platinum on the platinum particle surface, a total CO adsorption amount is measured, and assuming that the shape of the platinum particle is a cube, the particle diameter is estimated as a length of one side thereof. At this time, the estimation is made with an assumption that CO is not adsorbed on the carrier. In the case of the platinum-loaded alumina catalyst, CO is preferentially adsorbed on platinum, and the injection of CO is stopped immediately when the amount of discharged CO becomes equal to the amount of injected CO, but in the alumina carrier, the surface area is large and a certain amount of CO is adsorbed on the carrier, and therefore, this CO is estimated to be adsorbed on the platinum surface.

[0067] Here, the CO-pulse method will be described. When CO is pulsatively injected into a sample, CO is adsorbed on the surface of loaded metal and the amount of discharged CO is small in the early stage of the injection. After a while, CO is adsorbed on almost the entire surface of the loaded metal, and when a steady state is reached, almost all of the injected CO is discharged. At this time, the amount of discharged CO during adsorption is subtracted from the amount of discharged CO in the steady state, and the sum of the differences is obtained as the CO adsorption amount. The CO-pulse method is a method for calculating a metal surface area, dispersion ratio, and particle diameter from the adsorption amount and the loaded metal content. A concrete calculation method is described below.

[0068] From the CO gas amount Vt adsorbed by a sample amount of catalyst W (g) at a measurement temperature, the adsorption gas amount V per g of the catalyst at 0° C. was obtained from the following equation (1).

V=(Vt/W)×{273/(273+t)}(ml/g−cat)   (1)

[0069] Here, when the percentage of metal content of the sample is defined as C (%) and the atomic weight of the loaded metal is defined as M, the number of moles R of the loaded metal per g of the sample is obtained from the equation (2).

R=(C/100)×(1/M) (mol/g−cat)   (2) [0070] the number of moles K of the adsorption gas amount per g of the sample is obtained from the equation (3).

K=V/(22.4×10.sup.−3×10.sup.6) (mol/g−cat)   (3)

[0071] From these, the dispersion degree B (proportion of effective surface metal in the loaded metal) is obtained from the equation (4).

B=(K/R)×100 (%)   (4)

[0072] When the lattice constant of the loaded metal catalyst is defined as a (Å), and it is assumed that one adsorption gas molecule is adsorbed to a lattice constant area a.sup.2, the specific surface area S of the metal is obtained from the equation (5).

[00001]$\begin{array}{cc}& \left(5\right)\end{array}$$\begin{array}{c}S=\mathrm{the}\mathrm{number}\mathrm{of}\mathrm{gas}\mathrm{molecules}\mathrm{adsorbed}\mathrm{to}1g\mathrm{of}\mathrm{sample}\times a^2\\ =K\times 6.02\times 10^{23}\times {\left(a\times 10^{-10}\right)}^2\end{array}$

[0073] Further, when a loaded metal particle is assumed to be a cube with a side length D (m), five surfaces out of six surfaces of the particle are effective, and therefore, the following equations are established.

Effective area S of one particle=5D.sup.2 (m.sup.2)   (6)

Volume v of one particle=D3 (m.sup.3)   (7)

[0074] When the number of particles of the loaded metal per g of sample is defined as n, the following equations are established.

Specific surface area S of loaded metal=ns=n5D.sup.2 (m.sup.2)   (8)

Volume Vc of loaded metal=nv=Nd.sup.3 (m.sup.3)   (9)

[0075] From the equations (6) to (9), the length D (m) of one side is expressed by the equation (10).

S/Vc=5/D, and therefore, D=5Vc/S(m)   (10)

[0076] Here, when the percentage of loaded metal content is defined as C (%) and the specific gravity is defined as d (g/cm.sup.3), the volume Vc of the loaded metal per g of sample is expressed by the equation (11).

[00002]$\begin{array}{cc}\begin{array}{c}\mathrm{Vc}=\mathrm{loaded}\mathrm{metal}\mathrm{weight}\mathrm{per}g\mathrm{of}\\ \mathrm{sample}\left(g/g\right)/\mathrm{specific}\mathrm{gravity}\mathrm{of}\mathrm{loaded}\mathrm{metal}\left(g/{\mathrm{cm}}^3\right)\\ =C/100/d\left(g/{\mathrm{cm}}^3\right)\end{array}& \left(11\right)\end{array}$

[0077] Accordingly, the particle diameter is calculated from the equation (12).

[00003]$\begin{array}{cc}\begin{array}{c}\mathrm{particle}\mathrm{diameter}=5\mathrm{Vc}/S\\ =\left\{5\left(C/100/d\right)\times 10^{-6}\right\}/S\left(m\right)\\ =\left\{5\left(C/100/d\right)\times 10^{-6}\times 10^{10}\right\}/S\left(\AA \right)\end{array}& \left(12\right)\end{array}$

[0078] As described above, in the conventional platinum-loaded alumina catalyst, the particle diameter of the platinum loaded on the alumina carrier was measured (calculated) using the CO-pulse method or the transmission electron micrograph at that time (see FIG. 1(A)), in which error was relatively large. Therefore, in the conventional platinum-loaded alumina catalyst, the preferred range of the platinum particle diameter was set as a relatively wide range because it was difficult to control the platinum particle diameter with high accuracy.

[0079] In contrast to this, in the present invention, based on the value of the platinum particle diameter measured with relatively high accuracy according to the transmission electron micrograph in recent years (see FIG. 1(B)), a range of the platinum particle diameter (platinum particle diameter distribution) in which the catalyst life can be remarkably improved compared to the conventional platinum-loaded alumina catalyst is set. In the platinum-loaded alumina catalyst according to the present invention, it is preferred that 70% or more of the particles of platinum loaded on the γ-alumina carrier have a size of 8 to 15 Å in direct observation using the transmission electron microscope. More preferably, 80% or more of the particles of platinum loaded on the γ-alumina carrier have a size of 8 to 15 Å. Further preferably, 90% or more of the particles of platinum loaded on the γ-alumina carrier have a size of 8 to 15 Å.

[0080] Next, an egg shell-type metal-loaded catalyst and a uniform-type metal-loaded catalyst of the present invention will be described with reference to FIG. 2. The egg shell-type metal-loaded catalyst refers to a state where a metal member to be loaded is dispersed and loaded only on the outer shell part of the cross section of a molded catalyst. Namely, a metal loading part 2 on which the metal member is loaded is formed in the outer shell part of a porous carrier 1. The uniform-type metal-loaded catalyst refers to a state where a metal member is dispersed over the entire cross section of the catalyst and the metal loading part 2 on which the metal member is loaded is formed over the entire inside of a molded body of the porous carrier 1.

[0081] The platinum-loaded alumina catalyst according to the present invention includes an alumina carrier and platinum loaded on the alumina carrier.

[0082] Next, the alumina carrier used in the platinum-loaded alumina catalyst according to the present invention will be described.

[0083] The alumina carrier preferably is a porous γ-alumina carrier. More specifically, as disclosed in JPH6-72005B2, for example, the alumina carrier preferably is a porous γ-alumina carrier obtained by washing by filtration a slurry of aluminum hydroxide generated by neutralizing aluminum salt, dehydrating and drying the obtained alumina hydrogel, and then calcining the resultant at 400 to 800° C. for about 1 to 6 hours. More preferably, the alumina carrier is a porous γ-alumina carrier obtained through a pH swing process in which the pH of alumina hydrogel is alternately fluctuated between a pH range of the dissolution of alumina hydrogel and a pH range of the precipitation of boehmite gel and simultaneously an alumina hydrogel forming substance is added for growing crystals of the alumina hydrogel when the pH is fluctuated from at least either one of the pH ranges to the other one of the pH ranges. The porous γ-alumina carrier obtained through the pH swing process is excellent in the uniformity of pore distribution, and excellent in that the physical properties of each pellet are stable because there is less variation in the physical properties also in the alumina carrier pellet after the formation of the carrier.

[0084] The inventors of the present application made further study on the relationship between the drying and calcining conditions of the alumina hydrogel (boehmite) and the particle diameters of the loaded platinum and, as a result, found that to stably load many of the platinum particles on the γ-alumina carrier to have a size in the range of 8 to 15 Å, it is particularly preferred that the drying temperature is 200° C. or lower, the temperature of the calcination performed thereafter is 250 to 400° C., and the calcination time is 1 to 12 hours.

[0085] When preparing the uniform-type platinum-loaded alumina catalyst according to the present invention, there is no limitation on the sulfur or sulfur compound to be dispersed in the alumina carrier beforehand for incorporation thereof in so far as the sulfur or sulfur compound has a sulfur element and can be uniformly dispersed in the catalyst carrier during the preparation of the catalyst carrier of after the preparation of the catalyst carrier. For example, sulfur crystal powders, and sulfur-containing compounds such as sulfuric acid, and sulfate including ammonium sulfate can be mentioned as the sulfur or sulfur compound. From the viewpoint that sulfur is likely to disperse on a carrier, sulfur compounds having solubility in water or an organic solvent are preferable, and sulfuric acid, ammonium sulfate, etc. can be mentioned as such sulfur compounds.

[0086] The amount of sulfur to be contained in a carrier is preferably 0.15 to 5.0% by weight (wt %), and more preferably 0.15 to 3.0% by weight, calculated as elemental sulfur (S). When the sulfur content is less than 0.15% by weight, the degree that metal is uniformly loaded as far as the center of the catalyst is low, while when the sulfur content exceeds 5% by weight, a problem is likely to occur that sulfur is likely to locally agglomerate and metal is not dispersed and loaded on such a portion. In view of the above, the most suitable sulfur content range is 0.15 to 5.0% by weight considering the effect that metal is uniformly dispersed and loaded.

[0087] The inventors of the present application made further study on the relationship between the sulfur concentration and the particle diameters of the loaded platinum and, as a result, found that to stably load many of the platinum particles on the γ-alumina carrier to have a size in the range of 8 to 15 Å, it is particularly preferred that with respect to the range of sulfur content, sulfur or a sulfur compound is contained in a range of 0.5 to 1.2% by weight calculated as elemental sulfur (S).

[0088] In the present invention, with respect to a method of preparing a sulfur-containing catalyst carrier containing the above-mentioned sulfur or sulfur compound, usable is a method capable of incorporating the sulfur or sulfur compound in a state where the sulfur or sulfur compound is uniformly dispersed throughout the cross section of the carrier. For example, the following methods are mentioned: method A involving kneading sulfur powder in a metal hydroxide gel serving as a precursor of a metal oxide obtained when preparing a catalyst carrier, forming the resultant into a predetermined shape, and drying and calcining the resultant; method B involving preparing a metal hydroxide gel serving as a precursor of a metal oxide containing sulfur using metal sulfate and/or sulfuric acid when preparing a catalyst carrier, forming the resultant into a predetermined shape, and drying and calcining the resultant; method C involving forming a metal hydroxide gel serving as a precursor of a metal oxide into a predetermined shape when preparing a catalyst carrier, drying the resultant to form a dry metal hydroxide gel, impregnating the dry metal oxide with a sulfur compound solution, and calcining the same; method D involving forming a metal hydroxide gel serving as a precursor of a metal oxide into a predetermined shape when preparing a catalyst carrier, drying the resultant to form a dry metal hydroxide, impregnating the dry metal hydroxide with a sulfur compound solution, and calcining the same; and method E involving forming a metal hydroxide gel serving as a precursor of a metal oxide into a predetermined shape, drying the resultant to form a dry metal hydroxide gel, calcining the dry metal hydroxide gel to form a calcined metal oxide, impregnating the calcined metal oxide with a sulfur compound solution such as a sulfuric acid aqueous solution and an ammonium sulfate solution, and further calcining the resultant.

[0089] The inventors of the present application made further study on the method for preparing a sulfur-containing catalyst carrier and, as a result, found that to stably load many of the platinum particles on the γ-alumina carrier to have a size in the range of 8 to 15 Å, it is particularly preferred to disperse and load sulfur on the surface of the γ-alumina carrier according to the aforementioned method E.

[0090] With respect to calcining conditions when preparing the sulfur-containing catalyst carrier, usually, the calcining temperature is 100 to 1000° C., and preferably 350 to 800° C., and the calcining time is 0.5 to 48 hours, and preferably 1 to 24 hours. When the calcining temperature is lower than 350° C., conversion to an oxide from a hydroxide may not be fully performed, while when the calcining temperature is higher than 800° C., the surface area after calcining may be dramatically reduced.

[0091] The inventors of the present application made further study on the drying and calcining conditions when preparing a sulfur-containing γ-alumina carrier and, as a result, found that to stably load many of the platinum particles on the γ-alumina carrier to have a size in the range of 8 to 15 Å, it is particularly preferred that with respect to the drying condition, the drying temperature is 100 to 200° C. and the drying time is 3 to 12 hours, and with respect to the calcination condition, the calcination temperature 250 to 400° C. and the calcination time is 1 to 12 hours.

[0092] In the present invention, the amount of platinum to be loaded on the aforementioned sulfur-containing catalyst carrier is 0.05 to 5.0% by weight, preferably 0.1 to 3.0% by weight, calculated as elemental platinum. When the loading amount of platinum is less than 0.05% by weight, there is a problem that the activity is low, while when the loading amount of platinum exceeds 5.0% by weight, there are problems that the particle diameter of platinum increases, the selectivity is reduced, sintering is likely to occur, resulting in that deactivation is likely to occur.

[0093] The inventors of the present application made further study on the preferred loading amount of platinum and, as a result, found that to stably load many of the platinum particles on the γ-alumina carrier to have a size in the range of 8 to 15 Å, the loading amount of platinum is preferably 0.1 to 1.5% by weight calculated as content of elemental platinum, and more preferably, 0.5 to 1.5% by weight from the viewpoint of improvement of life of the prepared platinum-loaded alumina catalyst.

[0094] In the present invention, when platinum metal is loaded on the γ-alumina carrier, the above-mentioned γ-alumina carrier may be impregnated with a solution of platinum compound, dried, and then calcined at a predetermined temperature. As the platinum compound, chloride, bromide, ammonium salt, carbonyl compound, or various complex compounds, such as an amine complex, an ammine complex, and an acetylacetonato complex, of platinum can be mentioned. The platinum compound may be, for example, chloroplatinic acid, platinum acetylacetonate, ammonium platinate, bromo platinate, platinum dichloride, platinum tetrachloride hydrate, platinum carbonyl dichloride, dinitrodiamine platinate, or the like.

[0095] The inventors of the present application made further study on the platinum compound for impregnation and, as a result, found that from the viewpoint of improvement of life of the prepared platinum-loaded alumina catalyst, it is particularly preferred that the γ-alumina carrier after calcination is impregnated with platinum by using a chloroplatinic acid aqueous solution as a platinum reagent aqueous solution.

[0096] After the alumina carrier is impregnated with the above-mentioned solution of platinum compound, the alumina carrier to which the platinum compound adheres is dried at 50 to 200° C. for 0.5 to 48 hours, and thereafter is calcined at 350 to 600° C. for 0.5 to 48 hours, more preferably at 350 to 450° C. for 0.5 to 5 hours.

[0097] The inventors of the present application made further study on the drying and calcining conditions after suitable platinum impregnation to the alumina carrier (for example, the content calculated as elemental platinum is in a range of 0.5 to 1.5% by weight) and, as a result, found that to stably load many of the platinum particles on the γ-alumina carrier to have a size in the range of 8 to 15 Å, it is particularly preferred that with respect to the drying condition, the drying temperature is 100 to 200° C. and the drying time is 3 to 12 hours, and with respect to the calcination condition, the calcination temperature is 250 to 450° C. and the calcination time is 1 to 8 hours.

[0098] Then, as a final step of the platinum loading process, the alumina carrier to which the platinum compound adheres is placed in a hydrogen gas atmosphere and a hydrogen reduction process is performed under reduction condition at 350 to 600 ° C. for 0.5 to 48 hours, preferably at 350 to 550° C. for 3 to 24 hours. If the temperature during hydrogen reduction is lower than 350° C., a problem that platinum is not sufficiently reduced occurs, and if the temperature exceeds 600° C., a problem that the platinum particles are sintered during reduction and the metal dispersion degree is lowered occurs.

[0099] The inventors of the present application made further study on the temperature condition of the hydrogen reduction after suitable platinum impregnation and calcination and, as a result, found that to stably load many of the platinum particles on the γ-alumina carrier to have a size in the range of 8 to 15 Å, it is particularly preferred that the temperature of the hydrogen reduction is 300 to 450° C. and is lower than or equal to the temperature for calcination after platinum impregnation and that the hydrogen reduction time is 1 to 15 hours.

[0100] The amount of alkali that is added to the aforementioned egg shell-type platinum-loaded alumina catalyst and the uniform-type platinum-loaded alumina catalyst prepared by making sulfur contained in the γ-alumina carrier is 0.1 to 5% by weight, preferably 0.3 to 3.0% by weight, and more preferably 0.5 to 1.5% by weight. When the loading amount of alkali metal is less than 0.1% by weight, there is a problem that the catalyst life is short and the effect is low, while when the loading amount is more than 5.0% by weight, there is a problem that the activity is lowered and the catalyst life is shortened.

[0101] The inventors of the present application made further study on a preferred addition amount of alkali in loading many of the platinum particles on the γ-alumina carrier to have a size in the range of 8 to 15 Å and, as a result, found that so long as the addition amount of alkali is 0.5 to 1.5% by weight, there is no significant influence on the size of the platinum particles after preparation.

[0102] The compound of alkaline metal used when loading the alkaline metal to the egg shell-type platinum-loaded alumina catalyst and the uniform-type platinum-loaded alumina catalyst prepared by making sulfur contained in the γ-alumina carrier may be, for example, a chloride, bromide, iodide, nitrate, sulfate, acetate, propionic acid, and the like of, the alkaline metal, which preferably is water-soluble and/or soluble to an organic solvent such as acetone. Such a compound may be, for example, sodium chloride, sodium bromide, sodium iodide, sodium nitrate, sodium sulfate, sodium acetate, sodium propionate, potassium chloride, potassium bromide, potassium iodide, potassium nitrate, potassium sulfate, potassium acetate, potassium propionate, calcium chloride, calcium bromide, calcium iodide, calcium nitrate, calcium sulfate, calcium acetate, calcium propionate, or the like.

[0103] Also, when the alkaline metal is loaded on the egg shell-type platinum-loaded alumina catalyst and the uniform-type platinum-loaded alumina catalyst prepared by making sulfur contained in the γ-alumina carrier, they are impregnated with a solution of a compound of the alkaline metal, thereafter dried under a drying condition at room temperature to 200° C. for 0.5 to 48 hours, preferably at 50 to 150° C. for 0.5 to 24 hours, more preferably at 80 to 120° C. for 0.5 to 5 hours, and then calcined at 350 to 600° C. for 0.5 to 48 hours, preferably 350 to 450° C. for 0.5 to 5 hours.

[0104] The inventors of the present application made further study on the drying condition after the impregnation with a solution of a preferred alkali compound in loading many of the platinum particles on the γ-alumina carrier to have a size in the range of 8 to 15 Å and, as a result, found that so long as the temperature is at room temperature to 200° C., there is no influence on the size of the loaded platinum particles irrespective of the drying time.

[0105] The dried matter on which the alkali metal is loaded, which is obtained by impregnating the alkali metal into the egg shell-type platinum-loaded alumina catalyst and the uniform-type platinum-loaded alumina catalyst prepared by making sulfur contained in the γ-alumina carrier and drying the impregnated catalyst, is not calcined thereafter, and is directly subjected to final hydrogen reduction. The reduction condition of this hydrogen reduction is preferably at 350 to 600° C. for 0.5 to 48 hours, more preferably at 350 to 550° C. for 3 to 24 hours in a hydrogen gas atmosphere. If calcination is performed prior to the hydrogen reduction of the dried matter on which the alkali metal is loaded, there arises a problem that the catalyst performance related to activity, selectivity, and life is lowered. Also, if the temperature at the time of the hydrogen reduction is lower than 350° C., there arises a problem that platinum is not fully reduced, and if the temperature at the time of the hydrogen reduction exceeds 600° C., there arises a problem that sintering of platinum particles occurs at the time of reduction, and the metal dispersion degree is lowered.

[0106] The inventors of the present application made further study on the hydrogen reduction condition after the impregnation with a solution of a preferred alkali compound and drying in loading many of the platinum particles on the γ-alumina carrier to have a size in the range of 8 to 15 Å and, as a result, found that if the temperature and the reduction time are less than or equal to the temperature and the reduction time of the hydrogen reduction carried out as the final step of the platinum loading process before addition of the alkali metal, there is no influence on the size of the loaded platinum particles.

[0107] Hereinafter, preferable embodiments of the present invention will be specifically described based on Examples and Comparative Examples.

Comparative Example 1 (Comparison of Measurement Results of Particle Diameters of the Egg Shell-Type Catalysts Described in Patent Document 1 and the Uniform-Type Platinum-Loaded Alumina Catalysts Described in Patent Document 2 Between Direct Observation Using a Transmission Electron Microscope and the CO-Pulse Method)

[0108] The platinum particle diameters of the egg shell-type catalysts described in Patent Document 1 are particle diameters estimated based on the dispersion degree estimated from the CO adsorption amount measured by the CO-pulse method with the assumption that the shape of the platinum particle is a cube and, as shown in Table 2 (Experimental Example 1) and Table 3 (Experimental Example 2) of Patent Document 1, were estimated as particle diameters in a range of 5.5 to 14 Å.

[0109] On the other hand, the particle diameters of the uniform-type platinum-loaded alumina catalysts described in Patent Document 2 were estimated as particle diameters of 6.5 to 11 Å, as shown in Table 1 (Embodiment 4) of Patent Document 2.

[0110] As shown in FIG. 3, by direct observation using a transmission electron microscope, the particle diameters of 42 platinum particles (see the numbers 1-42 in FIG. 3) in a uniform-type platinum-loaded alumina catalyst described in Patent Document 2 were measured. The image of the catalyst shown in FIG. 3 corresponds to the transmission electron micrograph shown in FIG. 1(B). Also, this catalyst corresponds to the catalyst No. 6 (the particle diameter is 6.5 Å) described in Patent Document 2 (Table 1).

[0111] The measurement of platinum particle diameters can be performed by using a particle diameter measurement function on the screen of the electron microscope. Note, however, that it is also possible to obtain substantially the same measurement result by comparing the length of a part of the particle diameter having the largest diameter with a scale shown in the electron micrograph. Table 1 shows the measurement result of the particle diameters. The average particle diameter of the 42 platinum particles shown in Table 1 was 16.8 Å (1.68 nm).

TABLE-US-00001 TABLE 1 particle No. diameter (nm) 1 2.0 2 1.8 3 1.5 4 2.0 5 2.3 6 1.3 7 1.4 8 1.2 9 1.7 10 2.0 11 0.8 12 1.6 13 1.4 14 1.5 15 1.4 16 1.5 17 1.1 18 1.3 19 1.2 20 1.0 21 1.6 22 2.2 23 1.4 24 1.3 25 1.5 26 1.4 27 1.3 28 1.2 29 1.2 30 1.3 31 1.7 32 1.7 33 1.8 34 1.2 35 1.3 36 1.2 37 1.1 38 1 39 1.9 40 1.3 41 1.2 42 1.3 43 — 44 — 45 — 46 — 47 — 48 — 49 — 50 —

[0112] According to the measurement result of the platinum particle diameters shown in Table 1, it is seen that, of the 42 platinum particles measured, 19 (about 45%) platinum particles had a size in a range of 8 to 15 Å (0.8 to 1.5 nm), and 23 platinum particles were larger than 15 Å (1.5 nm) and had a size of 16 Å (1.6 nm) or larger.

[0113] Thus, when measured from the image for direct observation of the uniform-type platinum-loaded alumina catalyst described in Patent Document 2 (the catalyst No. 6 in Table 1 of Patent Document 2) taken by the electron microscope, the average particle diameter of platinum was 1.68 nm (16.8 Å). From this, it is seen that the estimated value (6.5 Å) of the particle diameter of platinum according to the CO-pulse method described in Patent Document 2 is a remarkably small value compared to the value measured by direct observation of the electron micrograph.

[0114] As described above, with respect to the egg shell-type catalysts described in Patent Document 1 and the uniform-type platinum-loaded alumina catalysts described in Patent Document 2, the particle diameters estimated based on the dispersion degree estimated from the CO adsorption amount measured by the CO-pulse method and the assumption that the shape of the platinum particle is a cube were estimated as particle diameters of 5.5 to 14 Å, but these particle diameters also are considered to be fairly small values according to the direct observation using the electron microscope.

[0115] The large error of the estimated value of the particle diameter obtained by the CO-pulse method like this is considered to be attributed to that in the CO-pulse method, the estimation is made on an assumption that the introduced CO is adsorbed on the platinum atoms exposed on the surface of platinum particles but actually there are many CO molecules adsorbed on the alumina carrier and therefore the CO adsorption amount is observed to be larger, and that the shape of the platinum particle is assumed to be a cube and the particle diameter is estimated as a length of one side thereof

Comparative Example 2 (Preparation Method Described in an Embodiment of Patent Document 1)

[0116] A preparation method of an egg shell-type platinum-loaded γ-alumina catalyst described in an embodiment of Patent Document 1 is explained.

[0117] Similarly to the embodiment of Patent Document 1, a porous γ-alumina carrier was produced according to the conventional technology described in Embodiment 1 of JPH6-72005B2. An outline of this method is as follows. A sodium aluminate aqueous solution was instantaneously added in hot dilute sulfuric acid while being vigorously stirred to obtain an aluminum hydroxide slurry suspension (pH10). This suspension was used as seed aluminum hydroxide and while stirring was continued, an operation of alternately adding the hot dilute sulfuric acid and the sodium aluminate aqueous solution at a constant interval was repeated to obtain filtered and washed cake. This cake was extruded and dried, and thereafter was calcined at 500° C. for 3 hours.

[0118] The γ-alumina carrier thus prepared physical properties of a surface area of 240 m.sup.2/g, a pore volume of 0.713 cm.sup.3/g, an average pore diameter of 119 Å, and an occupancy of pores with pore diameters 90 to 300 Å of 90%. 79 g of 0.4 wt %-chloroplatinic acid aqueous solution prepared so that the pH value was 2.0 was added to 20 g of this porous γ-alumina carrier, and this was left for 3 hours for impregnation before water was removed by decantation. Subsequently, the resultant was dried for 3 hours at 120° C. and then was calcined for 3 hours at 400° C. in a muffle furnace under air flow. The obtained calcined matter was cooled to normal temperature in the desiccator and thereafter was reduced at 400° C. for 15 hours under hydrogen flow to prepare a dehydrogenation catalyst (corresponds to the catalyst No. 2 in Table 2 of the embodiment of Patent Document 1). The estimated value of the platinum particle diameter of this catalyst according to the CO-pulse method was 5.5 Å.

Comparative Example 3 (Preparation Method Described in an Embodiment of Patent Document 2)

[0119] A preparation method of a uniform-type platinum-loaded γ-alumina catalyst described in an embodiment of Patent Document 2 is explained.

[0120] 3900 cc of aluminum nitrate aqueous solution with a concentration of 2.67 mol/L was prepared and simultaneously, 3900 cc of 14% aqueous ammonia solution was prepared. 20 L of pure water was put in a 30-L enamel container, and the container was warmed to 70° C. under stirring. While continuing stirring, a pH swing operation in which 1300 cc of aluminum nitrate aqueous solution was added, followed by stirring for 5 minutes (pH=2.0), and thereafter, 1300 cc of aqueous ammonia solution was added, followed by stirring for 5 minutes (pH=7.4) was performed 4 times. An aqueous slurry solution of the obtained aluminum hydroxide was filtered to recover a cake, and subsequently, a washing operation in which the cake was re-dispersed in 20 L of pure water and was filtered again was performed 3 times, obtaining a washed gel.

[0121] The washed cake was air dried to adjust the moisture, and then was formed into a rod-like shape having a diameter of 1.6 mm with an extruder. The resultant was dried (120° C., 3 hours), crushed to about 1 cm in length, and calcined in a muffle furnace (500° C., 3 hours), thereby yielding an alumina carrier A containing no sulfur. The obtained alumina carrier A had a BET surface area of 275 m.sup.2/g and a pore volume of 0.65 cm.sup.3/g as measured by mercury porosimetry. Also, the obtained alumina carrier A had an average pore diameter of 8.9 nm and had a sharp pore distribution in which almost all of the pores were concentrated near the average pore diameter. In addition, the volume occupied by pores having a diameter of 7 to 10 nm was 80% or more of the total pore volume.

[0122] The alumina carrier A was impregnated with an ammonium sulfate aqueous solution with a concentration of 0.38 mol/L so that the sulfur content after calcination was 0.5% by weight, and the solvent was removed with an evaporator. Thereafter, the alumina carrier A was dried (120° C., 3 hours) and calcined (500° C., 3 hours), thereby yielding an alumina carrier containing sulfur at 0.5% by weight.

[0123] The alumina carrier thus prepared was impregnated with a chloroplatinic acid aqueous solution whose pH was adjusted to 2.0 so that the loading amount of platinum after calcination was 0.6% by weight. Thereafter, moisture was removed with an evaporator, and the resultant was dried (120° C., 3 hours) and calcined (400° C., 3 hours). Then, the resultant was charged in a flow-type hydrogen-reducing apparatus, and hydrogen reduction was carried out at 450° C. for 15 hours in a hydrogen stream, thereby yielding a 0.6 wt % platinum-loaded alumina catalyst. The estimated value of the platinum particle diameter of this platinum-loaded alumina catalyst according to the CO-pulse method was 6.5 Å.

Comparative Example 4 (Reaction Test Method Related to the Egg Shell-Type Catalyst Described in Patent Document 1 and the Uniform-Type Catalyst Described in Patent Document 2)

[0124] Comparison of dehydrogenation reaction test methods and reaction test results related to the egg shell-type catalyst described in Patent Document 1 and the uniform-type catalyst described in Patent Document 2 is shown. Here, the dehydrogenation reaction test described in Patent Document 1 and the dehydrogenation reaction test described in Patent Document 2 differ with respect to the condition of reaction temperature and concentration of hydrogen supplied with the raw material MCH. This is because the deterioration speed is different between the dehydrogenation catalyst described in Patent Document 1 and the dehydrogenation catalyst described in Patent Document 2. The reaction test condition of the deterioration speed at the time of development of the dehydrogenation catalyst described in Patent Document 1 was a condition in which deterioration was relatively hard to progress. Specifically, the reaction test condition described in Patent Document 1 was a condition with a reaction temperature of 300° C. and a hydrogen supply concentration of 20%, whereas the reaction condition described in Patent Document 2 was a condition with a reaction temperature of 320° C. and a hydrogen supply concentration of 5%. The reason for this is that since the dehydrogenation catalyst described in Patent Document 2 is a catalyst having a low deterioration speed and hard to deteriorate, the reaction test was performed under an accelerated condition in which deterioration is easy to progress.

[0125] In this Comparative Example, with respect to the dehydrogenation reaction test of methylcyclohexane (MCH), the results of dehydrogenation reaction tests using the dehydrogenation catalyst described in Patent Document 1 as the catalyst NO. 1 and the dehydrogenation catalyst described in Patent Document 2 as the catalyst NO. 2 are shown.

[0126] 10 cc of each catalyst described above was put in a stainless steel reaction tube, which had an inside diameter of 12.6 mm and a length of 300 mm and which was equipped with a protection tube for a thermocouple whose outer dimension was ⅛ inch in the center of the cross section of the reaction tube, such that the center of the catalyst layer was positioned in a lengthwise center of the reaction tube, and 10 cc of spherical a-alumina beads with a diameter of 1 mm was placed on the upper side of the catalyst as a preheating layer. Under hydrogen flow (LHSV=5.0; 50 cc/hr), temperature was raised until the central temperature of the catalyst layer reaches 320° C. Subsequently, methylcyclohexane (MCH) in an amount corresponding to LHSV=2.0 (20 cc/hr) was supplied to the reactor with a liquid supply pump for high-speed liquid chromatography (HPLC) (HPLC pump), and immediately, the flow rate of hydrogen was adjusted so that the hydrogen gas amount was 5 mol % with respect to the total amount of MCH and hydrogen gas. The reaction test was performed while adjusting the output of an electric furnace so that the central temperature of the catalyst layer was 320° C. during the reaction.

[0127] A gas-liquid separator was provided at the outlet of the reaction tube, and the resultant was separated into a liquid product such as toluene and gas such as hydrogen gas, which were generated by the dehydrogenation reaction, and the collected liquid product and gas were separately analyzed by gas chromatography.

[0128] The MCH conversion rate (%), toluene selectivity (%), toluene yield (%), and produced methane concentration (ppm) 2 hours after and 300 hours after the initiation of the reaction were obtained. The results are shown in Table 2.

TABLE-US-00002 TABLE 2 after 24 hours from initiation of reaction after 300 hours from initiation of reaction plutinum MCH produced MCH produced sulfur loading conversion toluene toluene methane conversion toluene toluene methane catalyst content amount rate selectivity yield concentration rate selectivity yield concentration No. (wt %) (wt %) (%) (%) (%) (ppm) (%) (%) (%) (ppm) 1 0 0.6 98.2 99.88 98.1 180 94.5 99.9 94.4 115 2 0.5 0.6 98.2 99.92 98.1 50 97.7 99.93 97.6 35

Example 1 (Preparation Method and Particle Diameter Measurement Result of the Egg Shell-Type Catalyst According to the Present Invention)

[0129] 3900 cc of aluminum nitrate aqueous solution with a concentration of 2.67 mol/L was prepared and simultaneously, 3900 cc of 14% aqueous ammonia solution was prepared. 20 L of pure water was put in a 30-L enamel container, and the container was warmed to 70° C. under stirring. While continuing stirring, a pH swing operation in which 1300 cc of aluminum nitrate aqueous solution was added, followed by stirring for 5 minutes (pH=2.0), and thereafter, 1300 cc of aqueous ammonia solution was added, followed by stirring for 5 minutes (pH=7.4) was performed 4 times. An aqueous slurry solution of the obtained aluminum hydroxide was filtered to recover a cake, and subsequently, a washing operation in which the cake was re-dispersed in 20 L of pure water and was filtered again was performed 3 times, obtaining a washed gel.

[0130] The washed cake was air dried to adjust the moisture, and then was formed into a rod-like shape having a diameter of 1.6 mm with an extruder. The resultant was dried (120° C., 3 hours), crushed to about 1 cm in length, and calcined in a muffle furnace (350° C., 3 hours), thereby yielding an alumina carrier A containing no sulfur. The obtained alumina carrier A had a BET surface area of 290 m.sup.2/g and a pore volume of 0.61 cm.sup.3/g as measured by mercury porosimetry. Also, the obtained alumina carrier A had an average pore diameter of 9.5 nm (95 Å) and had a sharp pore distribution in which almost all of the pores were concentrated near the average pore diameter. In addition, the volume occupied by pores having a diameter of 7 to 11 nm (70 to 110 Å) was 80% or more of the total pore volume.

[0131] The alumina carrier thus prepared was impregnated with a chloroplatinic acid aqueous solution whose pH was adjusted to 2.0 so that the loading amount of platinum after calcination was 0.6% by weight. Thereafter, moisture was removed with an evaporator, and the resultant was dried (120° C., 3 hours) and calcined (350° C., 3 hours). Then, the alumina carrier was placed in a flow-type hydrogen-reducing apparatus, and hydrogen reduction was carried out at 400° C. for 15 hours in a hydrogen stream, thereby yielding a 0.6 wt % platinum-loaded alumina catalyst (hereinafter referred to as a catalyst NO. 3). In the catalyst NO. 3 thus obtained, the average particle diameter of the platinum particles as measured by direct observation using an electron microscope was 11.27 Å. Table 3 shows the measurement result of the platinum particle diameter.

TABLE-US-00003 TABLE 3 particle No. diameter (nm) 1 1.5 2 0.9 3 1.3 4 1.5 5 1.3 6 1.1 7 1.2 8 1.9 9 1.5 10 1.2 11 1.0 12 1.4 13 1.4 14 1.8 15 1.4 16 1.3 17 0.9 18 1.1 19 1.0 20 0.9 21 1.4 22 1.7 23 1.2 24 0.8 25 1.3 26 1.5 27 1.1 28 1.2 29 1.0 30 1.1 31 1.5 32 1.5 33 2.1 34 1.0 35 1.1 36 1.0 37 1.5 38 0.8 39 1.6 40 1.1 41 1.0 42 1.1 43 1.4 44 1.2 45 1.3 46 — 47 — 48 — 49 — 50 —

[0132] In Table 3, it is seen that the smallest platinum particle was 8 Å (0.8 nm) in size, and the largest platinum particle was 21 Å (2.1 nm) in size. Also, of the 45 platinum particles measured, 40 (about 89%) platinum particles had a size in a range of 8 to 15 Å (0.8 to 1.5 nm), and only 5 platinum particles were larger than 15 Å (1.5 nm) and had a size of 16 Å (1.6 nm) or larger.

Example 2 (Preparation Method and Particle Diameter Measurement Result of the Uniform-Type Catalyst According to the Present Invention)

[0133] 3900 cc of aluminum nitrate aqueous solution with a concentration of 2.67 mol/L was prepared and simultaneously, 3900 cc of 14% aqueous ammonia solution was prepared. 20 L of pure water was put in a 30-L enamel container, and the container was warmed to 70° C. under stirring. While continuing stirring, a pH swing operation in which 1300 cc of aluminum nitrate aqueous solution was added, followed by stirring for 5 minutes (pH=2.0), and thereafter, 1300 cc of aqueous ammonia solution was added, followed by stirring for 5 minutes (pH=7.4) was performed 4 times. An aqueous slurry solution of the obtained aluminum hydroxide was filtered to recover a cake, and subsequently, a washing operation in which the cake was re-dispersed in 20 L of pure water and was filtered again was performed 3 times, obtaining a washed gel.

[0134] The washed cake was air dried to adjust the moisture, and then was formed into a rod-like shape having a diameter of 1.6 mm with an extruder. The resultant was dried (120° C., 3 hours), crushed to about 1 cm in length, and calcined in a muffle furnace (350° C., 3 hours), thereby yielding an alumina carrier A containing no sulfur. The obtained alumina carrier A had a BET surface area of 290 m.sup.2/g and a pore volume of 0.61 cm.sup.3/g as measured by mercury porosimetry. Also, the obtained alumina carrier A had an average pore diameter of 9.5 nm (95 Å) and had a sharp pore distribution in which almost all of the pores were concentrated near the average pore diameter. In addition, the volume occupied by pores having a diameter of 7 to 11 nm (70 to 110 Å) was 80% or more of the total pore volume.

[0135] The γ-alumina carrier thus prepared was impregnated with an ammonium sulfate aqueous solution with a concentration of 0.38 mol/L so that the sulfur content after calcination was 0.5% by weight, and after the solvent was removed with an evaporator, the resultant was dried (120° C., 3 hours) and calcined (350° C., 3 hours), thereby yielding an alumina carrier containing sulfur.

[0136] The obtained alumina carrier was impregnated with a chloroplatinic acid aqueous solution whose pH was adjusted to 2.0 so that the loading amount of platinum after calcination was 0.6% by weight. Thereafter, moisture was removed with an evaporator, and the resultant was dried (120° C., 3 hours) and calcined (350° C., 3 hours). Then, the alumina carrier was placed in a flow-type hydrogen-reducing apparatus, and hydrogen reduction was carried out at 400° C. for 15 hours in a hydrogen stream, thereby yielding a 0.6 wt % platinum-loaded alumina catalyst (hereinafter referred to as a catalyst NO. 4). In the catalyst NO. 4 thus obtained, the average particle diameter of the platinum particles as measured by direct observation using an electron microscope was 11.27 Å. Table 4 shows the measurement result of the platinum particle diameter.

TABLE-US-00004 TABLE 4 particle No. diameter (nm) 1 1.3 2 1.5 3 1.4 4 1.9 5 1.4 6 1.2 7 1.3 8 1.1 9 1.5 10 1.8 11 0.8 12 1.7 13 1.5 14 1.5 15 1.5 16 1.4 17 1.0 18 1.2 19 1.1 20 1.0 21 1.5 22 1.3 23 1.3 24 1.2 25 1.4 26 2.2 27 1.2 28 1.1 29 1.1 30 1.2 31 1.5 32 1.4 33 1.7 34 1.1 35 1.2 36 0.8 37 1.0 38 1.2 39 1.4 40 1.2 41 1.4 42 1.5 43 1.6 44 1.3 45 1.2 46 1.4 47 1.3 48 — 49 — 50 —

[0137] In Table 4, the smallest platinum particle was 8 Å (0.8 nm) in size, and the largest platinum particle was 22 Å (2.2 nm) in size. Also, of the 47 platinum particles measured, 41 (about 87%) platinum particles had a size in a range of 8 to 15 Å (0.8 to 1.5 nm), and only 6 platinum particles were larger than 15 Å (1.5 nm) and had a size of 16 Å (1.6 nm) or larger.

Example 3 (Reaction Test Results of the Egg Shell-Type Catalyst and the Uniform-Type Catalyst According to the Present Invention)

[0138] For the egg shell-type platinum-loaded γ-alumina catalyst prepared under the preparation condition according to the present invention shown in Example 1 (catalyst NO. 3) and the uniform-type platinum-loaded γ-alumina catalyst prepared under the preparation condition according to the present invention shown in Example 2 (catalyst NO. 4), the dehydrogenation reaction test of methylcyclohexane was carried out according to the method and reaction condition similar to the method shown in Comparative Example 4. Table 5 shows the results of the dehydrogenation reaction test together with the average particle diameter of the platinum particles measured based on direct observation of the images taken by the electron microscope and the results of calculating the ratio of the number of platinum particles having a size in a range of 8 to 15 Å among the platinum particles measured.

TABLE-US-00005 TABLE 5 after 24 hours from after 300 hours from ratio of plutinum initiation of reaction initiation of reaction plutinum average particles having plutinum MCH MCH particle diameter (Å) diameter in a sulfur loading conversion toluene toluene conversion toluene toluene direct range of 8-15 Å as catalyst content amount rate selectivity yield rate selectivity yield CO-pulse observation measured by No. (wt %) (wt %) (%) (%) (%) (%) (%) (%) method method direct observation (%) 1 0 0.6 98.2 99.88 98.1 94.5 99.90 94.4 5.5 — 2 0.5 0.6 98.2 99.92 98.1 97.7 99.93 97.6 6.5 16.8 45.2 3 0 0.6 98.4 99.91 98.3 96.2 99.90 96.1 — 12.7 88.9 4 0.5 0.6 98.4 99.95 98.4 98.1 99.93 98.0 — 13.4 84.4

[0139] As seen from the reaction test results of Table 5, as a result of optimizing the condition of catalyst preparation according to the present invention, platinum-loaded alumina catalysts having excellent performance particularly in the catalyst life were obtained. Compared to the egg shell-type platinum-loaded γ-alumina catalyst prepared under the conventional preparation condition (catalyst NO. 1), the egg shell-type platinum-loaded γ-alumina catalyst prepared under the preparation condition according to the present invention (catalyst NO. 3) is smaller in the reduction of toluene yield and has a longer life. Also, compared to the uniform-type platinum-loaded γ-alumina catalyst prepared under the conventional preparation condition (catalyst NO. 2), the uniform-type platinum-loaded γ-alumina catalyst prepared under the preparation condition according to the present invention (catalyst NO. 4) is smaller in the reduction of toluene yield and has a longer life.

[0140] Since the reaction test of Table 5 was carried out under the accelerated test condition, the amount of deterioration of toluene yield after about 300 hours appears small. However, the amount of deterioration under the accelerated test condition is remarkably larger than the amount of deterioration under the actual reaction condition in commercialization, and roughly speaking, while the life of the catalyst NO. 1 in Table 5 is about one year and the life of the catalyst NO. 2 is about two years, the life of the catalyst NO. 3 can be expected to be about three years, and the life of the catalyst NO. 4 can be expected to be about four years.

[0141] In addition, in the catalysts according to the present invention (catalyst NO. 3, catalyst NO. 4) in which the catalyst life is improved by the preparation methods shown in Example 1 and Example 2, among the all platinum particles for which the platinum particle diameter was measured by direct observation of the observation image taken by the electron microscope, 80% or more of the platinum particles had a particle diameter in the range of 8 to 15 Å. Compared to the catalyst NO. 2 in which the ratio of the number of particles having a particle diameter in the range of 8 to 15 Å was about 45%, it is seen that in the catalysts according to the present invention, the ratio of the number of platinum particles having a particle diameter in the range of 8 to 15 Å is significantly high and the ratio of the platinum particles having a size of 16 Å or greater is remarkably decreased.

[0142] The reason that the catalyst life of the catalysts prepared by the preparation methods shown in Example 1 and Example 2 according to the present invention (catalyst NO. 3, catalyst NO. 4) was conspicuously improved as described above is considered to be that the calcination condition when preparing the γ-alumina carrier, the calcination condition after impregnating platinum (and sulfur, if necessary) and drying, and the condition when finally carrying out hydrogen reduction were optimized.

[0143] The reason that the life of the conventional catalysts (namely, the dehydrogenation catalysts described in Patent Document 1 and Patent Document 2) was hindered is considered to be that in the conventional preparation method, the calcination condition when preparing the γ-alumina carrier was over 400° C., the calcination condition after impregnating platinum (and sulfur, if necessary) and drying was similarly at high temperature, and the final hydrogen reduction temperature was high similarly to the calcination conditions when preparing the carrier and after impregnation of platinum (and sulfur, if necessary) and drying. Particularly, it was found to be more preferable that in the preparation of the catalyst, the final hydrogen reduction temperature is set to 400° C. or lower and the calcination which causes thermal history before the hydrogen reduction is carried out at a temperature lower than the final hydrogen reduction condition.

[0144] Note that the catalysts according to the present invention cannot be accomplished with the electron microscope technology that could be used for the conventional catalysts (namely, at the time of filing of patent applications related to the dehydrogenation catalysts described in Patent Document 1 and Patent Document 2), and could be accomplished due to evolution of the electron microscope technology thereafter in which the electron microscope technology has been progressed to enable the size of the platinum particles of the catalysts prepared under various catalyst preparation conditions to be accurately measured by direct observation.

INDUSTRIAL APPLICABILITY

[0145] The egg shell-type platinum-loaded alumina catalyst and the uniform-type platinum-loaded alumina catalyst according to the present invention can be favorably used in the dehydrogenation reaction of hydrogenated aromatics such as methylcyclohexane used as a hydrogen energy carrier, and can contribute to practical implementation of the hydrogen storage and transportation system according to the organic chemical hydride method. Besides, there is a possibility that they can be widely applied to the existing catalytic reaction processes in which the platinum-loaded alumina catalyst is used. Thus, the present invention has very high industrial applicability. LIST OF REFERENCE NUMERALS [0146] 1 carrier [0147] 2 metal loading part