EGG SHELL-TYPE PLATINUM-LOADED ALUMINA CATALYST, METHOD OF PRODUCING SAME, AND METHOD OF USING SAME

Abstract

To provide an egg shell-type platinum-loaded alumina catalyst demonstrating excellent performance in terms of catalyst life, an egg shell-type platinum-loaded alumina catalyst includes: an alumina carrier; platinum dispersed and loaded on an outer shell of the alumina carrier; and one or more second components selected from the group consisting of vanadium, chromium, molybdenum, and phosphorus. Preferably, the content of platinum is 0.05 to 5.0 wt % calculated as elemental platinum. The content of each second component preferably is 0.1 to 5.0 wt % calculated as each element. The alumina carrier has a surface area of 150 m.sup.2/g or more, a pore volume of 0.40 cm.sup.3/g or more, and an average pore diameter of 40 to 300 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.

Claims

1. An egg shell-type platinum-loaded alumina catalyst, comprising: an alumina carrier; platinum dispersed and loaded on an outer shell of the alumina carrier; and one or more second components selected from the group consisting of vanadium, chromium, molybdenum, and phosphorus.

2. The egg shell-type platinum-loaded alumina catalyst according to claim 1, wherein a content of the platinum is 0.05 to 5.0 wt % calculated as elemental platinum.

3. The egg shell-type platinum-loaded alumina catalyst according to claim 1, wherein a content of each second component is 0.1 to 5.0 wt % calculated as each element.

4. The egg shell-type platinum-loaded alumina catalyst according to claim 1, wherein the alumina carrier has a surface area of 150 m2/g or more, a pore volume of 0.40 cm3/g or more, and an average pore diameter of 40 to 300 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.

5. A method of producing an egg shell-type platinum-loaded alumina catalyst, comprising: a step of impregnating an alumina carrier with an aqueous solution of compound containing one or more components selected from the group consisting of vanadium, chromium, molybdenum, and phosphorus, and thereafter performing drying and calcination; a step of loading platinum on the alumina carrier after calcination in an egg shell form; and a step of reducing the alumina carrier on which platinum is loaded in a hydrogen atmosphere.

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

7. The method of dehydrogenating a hydrogenated aromatic according to claim 6, 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.

8. The method of dehydrogenating a hydrogenated aromatic according to claim 6, wherein the hydrogenated aromatic is one member or a mixture of two or more members selected from the group consisting of methylcyclohexane, cyclohexane, dimethylcyclohexane, tetralin, decalin, methyldecalin, biphenyl, diphenylmethyl, dibenzotriol, and tetradecahydroanthracene.

9. The method of dehydrogenating a hydrogenated aromatic according to claim 6, which uses both of the egg shell-type platinum-loaded alumina catalyst and a uniform-type platinum-loaded alumina catalyst.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0029] FIG. 1 is an explanatory diagram showing (A) an egg shell-type metal-loaded catalyst and (B) a uniform-type metal-loaded catalyst.

MODE(S) FOR CARRYING OUT THE INVENTION

[0030] First, 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. 1. 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.

[0031] The uniform-type platinum-loaded alumina catalyst includes an alumina carrier, sulfur or a sulfur compound dispersed over the entire cross section of the alumina carrier, platinum dispersed and loaded over the entire cross section of the alumina carrier, and one or more alkali metals selected from the group consisting of sodium, potassium, and calcium.

[0032] Next, the alumina carrier used in the present invention will be described. The alumina carrier has a surface area of 150 m.sup.2/g or more, a pore volume of 0.40 cm.sup.3/g or more, and an average pore diameter of 40 to 300 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.

[0033] The alumina carrier preferably is a porous γ-alumina carrier. 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.

[0034] In the present invention, the amount of addition of the second component loaded on the aforementioned alumina carrier is 0.1 to 5.0 wt %, preferably 0.3 to 3.0 wt %, and more preferably 0.5 to 2.0 wt %. If the loading amount of the second component is less than 0.1 wt %, there is a problem that the catalyst life is short and the effect is insignificant, while if the loading amount of the second component is greater than 5.0 wt %, there arises a problem that the activity becomes lower and the catalyst life becomes short.

[0035] The compound of the second component used when adding the second component to the aforementioned alumina carrier may be, for example, a chloride, bromide, iodide, nitrate, sulfate, acetate, propionic acid, and the like of the second component element, which preferably is water soluble and/or soluble to an organic solvent such as acetone. Such a compound may be, for example, vanadium chloride, vanadium bromide, vanadium iodide, ammonium metavanadate, vanadyl chloride, vanadyl sulfate, vanadium oxide acetyl acetate, chromium chloride, chromium bromide, chromium iodide, chromium nitrate, chromium sulfate, chromium acetate, chromium propionate, molybdenum chloride, molybdenum bromide, molybdenum iodide, molybdates, phosphoric acid, inorganic phosphate such as ammonium dihydrogen phosphate, organophosphate compound, or the like.

[0036] Also, when the second component element is added to the egg shell-type platinum-loaded alumina catalyst, it is desirable that the egg shell-type platinum-loaded alumina catalyst is impregnated with a solution of a second component element compound, 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, and 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, more preferably at 350 to 450° C. for 0.5 to 5 hours.

[0037] In the present invention, the amount of platinum to be loaded on the aforementioned alumina carrier on which the second component is loaded is 0.05 to 5.0 wt %, preferably 0.1 to 3.0 wt %, calculated as elemental platinum. When the loading amount of platinum is less than 0.05 wt %, there is a problem that the activity is low, while when the loading amount of platinum exceeds 5.0 wt %, 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.

[0038] In the present invention, when platinum metal is loaded on the alumina carrier, the above-mentioned 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 salt, or the like.

[0039] 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. Then, the calcined alumina carrier is subjected to hydrogen reduction treatment in a hydrogen gas atmosphere under a 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 this hydrogen reduction is lower than 350° C., there is a problem that platinum may not be sufficiently reduced, while if the temperature during the hydrogen reduction exceeds 600° C., there is a problem that sintering of platinum particles occurs at the time of reduction and the metal dispersion degree decreases.

[0040] The method of producing the egg shell-type platinum-loaded alumina catalyst includes a step of impregnating the alumina carrier with an aqueous solution of compound containing one or more components selected from the group consisting of vanadium, chromium, molybdenum, and phosphorus, and thereafter performing drying and calcination, a step of loading platinum on the alumina carrier after calcination in an egg shell form, and a step of reducing the alumina carrier on which platinum is loaded in a hydrogen atmosphere.

[0041] In the cost reduction of dehydrogenation catalyst for the organic chemical hydride method/system, it is conceivable, next to extension of the catalyst life, to simplify the process by non-use of sulfur. The present inventors carried out extensive research on dehydrogenation catalyst which can achieve similar catalyst life without use of sulfur, and found that similar effect can be obtained by adding, instead of alkali metal or sulfur, a component selected from vanadium, chromium, molybdenum, and phosphorus as a second component other than platinum, thereby to complete the present invention.

[0042] Patent Document 1 discloses an egg shell-type platinum-loaded alumina catalyst in which platinum is loaded on an alumina carrier having a physical property of a surface area of 150 m.sup.2/g or more, a pore volume of 0.40 cm.sup.3/g or more, and an average pore diameter of 40 to 300 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, such that 0.1 to 3 wt % of platinum calculated as elemental platinum is dispersed and loaded on an outer shell of the carrier cross section, as well as a catalyst obtained by adding alkali metal to this catalyst.

[0043] Namely, the present inventors found that by adding, instead of alkali metal, a component selected from vanadium, chromium, molybdenum, and phosphorus as a second component other than platinum to the egg shell-type platinum-loaded alumina catalyst disclosed in Patent Document 1, superior catalyst performance, particularly superior catalyst life, can be achieved compared to the alkali metal-added egg shell-type platinum-loaded alumina catalyst, thereby to complete the present invention.

[0044] The egg shell-type platinum-loaded alumina catalyst of the present invention is used, for example, as a dehydrogenation catalyst for a hydrogenated aromatic, which is utilized as a hydrogen energy carrier in the organic chemical hydride method, which is one of the methods for storing and transporting the hydrogen energy. The hydrogenated aromatic preferably 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. Also, the hydrogenated aromatic preferably is one member or a mixture of two or more members selected from the group consisting of methylcyclohexane, cyclohexane, dimethylcyclohexane, tetralin, decalin, methyldecalin, biphenyl, diphenylmethyl, dibenzotriol, and tetradecahydroanthracene.

[0045] When the platinum-loaded alumina catalyst is used in the dehydrogenation reaction of a hydrogenated aromatic such as methylcyclohexane in the organic chemical hydride method, catalyst deterioration is observed, in which the performance decreases gradually as the reaction time passes. The cause of the catalyst deterioration is carbon precipitation called coking. Coking is a phenomenon in which carbon precipitation occurs on the surface of platinum metal, which is an active metal mainly due to decomposition reaction of the raw material compound such as methylcyclohexane, and as a result, the effective active sites of the active metal are covered and do not function.

[0046] The catalytic reaction deterioration phenomenon is observed as a decrease of the conversion rate in the reaction test, and in the case of dehydrogenation reaction of a hydrogenated aromatic, it is known that the phenomenon is observed as a linear decrease of the conversion rate. Accordingly, by observing the change of the conversion rate over time in the reaction test, it is possible to evaluate relative superiority or inferiority of the catalyst life based on the inclination of the decrease. Further, since the conversion rate decreases linearly not only under actual reaction conditions but also in an accelerated reaction test for evaluating the catalyst life in a short time, it is possible to evaluate the catalyst life.

[0047] Hydrogen attracted attention as clean secondary energy from 1970s, and in Japan, research and development of hydrogen production technologies and fuel cells were promoted in the Sunshine Project from 1974 to 1992, the Moonlight Project from 1978 to 1992, and the New Sunshine Project from 1993 to 2001. Regarding large-scale storage and transportation technology of hydrogen, development of liquefied hydrogen method was started in the WE-NET project from 1992 to 2002. On the other hand, the history of development of the organic chemical hydride method is old, and goes back to the Euro-Quebec project which was carried out in 1980s as an international research and development project by Canada's Quebec government and twelve European countries. This plan proposed producing hydrogen by performing water electrolysis by using excess hydroelectric power abundantly present in Quebec and transporting the hydrogen across the Atlantic Ocean for use in Europe. As a hydrogen transportation method, discussion was made on the liquid hydrogen method as a first candidate, the liquid ammonia method as a second candidate, and the organic chemical hydride method as a third candidate. At that time, the organic chemical hydride method was called an MCH method. The Euro-Quebec project continued till about 1992 for approximately 10 years but the project ended with none of the methods being practically implemented, and since then, technology for large-scale hydrogen store and transport has not been practically implemented.

[0048] In Japan, development of the liquefied hydrogen method was promoted in WE-NET project implemented from 1992 to 2002, while the research of the organic chemical hydride method was promoted mainly by Japanese universities. The applicant started the development of dehydrogenation catalyst in 2002 and made a first academic presentation in the World Hydrogen Energy Conference held in Yokohama in 2004, and from around this time, examples of research and development at companies were started to be released. At the present time, the large-scale hydrogen storage and transportation technologies for which research and development have been advanced to a demonstration level are only the liquefied hydrogen method and the organic chemical hydride method, which is proposed by the applicant.

[0049] The organic chemical hydride method (OCH method) is a method in which hydrogen is subjected to hydrogenation reaction with an aromatic such as toluene (TOL) and converted to a saturated cyclic compound such as methylcyclohexane (MCH) having the hydrogen taken in the molecule thereof so that “storage” and “transportation” are achieved in a liquid state under normal temperature and normal pressure and a necessary amount of hydrogen is taken out by dehydrogenation reaction and used at the place of use. Thus, the method includes a hydrogenation reaction (hydrogen storage reaction) for making hydrogen react with toluene and a dehydrogenation reaction (hydrogen generation reaction) for generating hydrogen from MCH and recovering toluene. TOL generated after taking out hydrogen is recovered and repeatedly used as a container (carrier) of hydrogen.

[0050] Since hydrogen is an explosive gas, there is a potentially high risk in storing and transporting hydrogen as it is in a large scale. In the present method, storage and transportation of hydrogen is performed with the hydrogen being retained in the molecule of MCH, which is a component of gasoline and diesel oil and is in the liquid state under normal temperature and normal pressure, and therefore, this method is highly safe in principle. Specifically, even if the tank and the reactor of the present system are caught in a fire, it would be similar to conventional oil refinery fires, and it is considered that the possibility of causing severe damage to the surrounding urban area is very low. The thought “accidents will eventually happen” is very important to safety measures, and that is why it is required to be safe in principle.

[0051] With this method, it is possible to store about 530 L of hydrogen gas in 1 L of liquid MCH. To physically decrease the volume of hydrogen gas to 1/500 or less, it is necessary to compress the hydrogen gas to 500 atm or higher or to cool the hydrogen gas to −253° C. or lower to make it liquid hydrogen which is 1/800 in volume, but according to the present method, by use of chemical reaction it is possible to decrease the volume to 1/500 under normal temperature and normal pressure. Also, since TOL and MCH are in the liquid state in a wide temperature range of −95 to 101° C., they can be handled as a liquid such as water under any environment on the Earth. To establish a large-scale supply chain, it is necessary to procure hundreds of thousands of tons of TOL, but TOL is a fuel base material contained in high octane gasoline in a proportion of 10 wt % or more and also is a general purpose chemical product produced in 20 million tons per year worldwide to be used widely as industrial solvent. Therefore, TOL can be easily procured in large amounts.

[0052] From the foregoing, the primary feature of the present method is high safety that can lower the potential risk regarding large-scale storage and transportation of hydrogen to the level of the risk related to conventional gasoline storage and transportation in principle, and this is the first reason why the applicant focused on this method. Also, storage of TOL and MCH in large tanks and transportation of the same by chemical tankers and chemical lorries have been practically implemented from old times as chemical products. In the current trend of electrification of automobiles, demand for gasoline and diesel oil as automobile fuels is expected to decrease and the existing infrastructure therefor, such as storage tanks, could be diverted. This can be a significant merit.

[0053] Further, in a case where hydrogen is used in large scale as fuel for power generation in the future, it is expected that hydrogen fuel reserve will become necessary as the current oil reserve. TOL and MCH do not chemically change even if stored for a long period and in large scale, and there is no extra energy consumption or loss due to long-term storage, and therefore, by storing MCH in the tanks of current oil reserve base, it is possible to convert the oil reserve bae to a reserve base for hydrogen energy.

[0054] The applicant focused on the organic chemical hydride method which has the highest safety and is advantageous in cost because the existing infrastructure can be diverted, started the development of novel dehydrogenation catalyst, which is the key to practical implementation, in 2002, and succeeded first in the world in developing novel dehydrogenation catalyst that can be industrially applicable to the organic chemical hydride method. Thereafter, for the purpose of establishment of technology for the whole system, the applicant used the developed catalyst in the dehydrogenation process and combined it with the toluene hydrogenation process, which realizes hydrogen storage reaction, to construct a demonstration plant which continuously repeats the hydrogen storage and hydrogen generation at the same place in 2013. The demonstration operation was conducted from April 2013 to November 2014 for about 10,000 hours in total, and it was confirmed that high performance as designed could be maintained stably, whereby the establishment of the technology was completed.

[0055] Thereafter, as the final stage of the development, a first-in-the-world demonstration of international hydrogen supply chain, in which about 200 tons of hydrogen will be actually transported from Brunei in Southeast Asia to Kawasaki waterfront in Japan by use of the present system, will be carried out as a project of NEDO (New Energy and Industrial Technology Development Organization) in 2020.

[0056] Japan has adopted a policy to promote practical implementation and dissemination of hydrogen energy as a national policy from the Fourth Strategic Energy Plan after the Great East Japan Earthquake, and following formulation of the Hydrogen Fuel Cell Technology Roadmap, the Hydrogen Basic Strategy was approved by the cabinet in 2017. Practical implementation of the aforementioned organic chemical hydride method is incorporated, as a hydrogen energy carrier for “storing” and “transporting” hydrogen energy in a large scale, in the Hydrogen Basic Strategy, which sets 30 ¥/Nm.sup.3 as a target hydrogen supply price by 2030, and 20 ¥/Nm.sup.3 by 2050. This requires cost reduction by continuous improvement technology development, and improvement of the catalyst performance is an important element of the cost reduction. Thus, the present invention is effective in the practical implementation of the organic chemical hydride method and highly useful industrially.

[0057] The egg shell-type platinum-loaded alumina catalyst not only can be used as a catalyst but also can be effectively used as an adsorbent or the like. The uniform-type platinum-loaded alumina catalyst is also useful as a filler of guard columns for preprocessing of adsorbing impurities and the like in the catalytic reaction process to which the catalyst of the present invention can be applied, as application to the organic chemical hydride method.

[0058] The egg shell-type platinum-loaded alumina catalyst according to the present embodiment may be used together with a uniform-type alkali-added platinum-loaded alumina catalyst. The uniform-type alkali-added platinum-loaded alumina catalyst preferably includes an alumina carrier, sulfur or a sulfur compound dispersed over an entire cross section of the alumina carrier, platinum dispersed and loaded over the entire cross section of the alumina carrier, and one or more alkali metals selected from the group consisting of sodium, potassium, and calcium. The alumina carrier preferably has a surface area of 150 m.sup.2/g or more, a pore volume of 0.40 cm.sup.3/g or more, and an average pore diameter of 40 to 300 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. The amount of sulfur to be contained in the carrier is preferably 0.15 to 5 wt %, and more preferably 0.15 to 3.0 wt %, calculated as elemental sulfur. The most suitable sulfur content range is 0.15 to 3.0 wt. The loading amount of platinum is 0.05 to 5.0 wt %, preferably 0.1 to 3.0 wt %. The amount of alkali added is 0.1 to 5 wt %, preferably 0.3 to 3.0 wt %, and more preferably 0.5 to 1.5 wt %. The compound of the alkaline metal used when loading the alkaline metal to the uniform-type platinum-loaded alumina catalyst 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.

[0059] The egg shell-type platinum-loaded alumina catalyst and the uniform-type alkali-added platinum-loaded alumina catalyst are preferably charged in the same reactor. The egg shell-type platinum-loaded alumina catalyst and the uniform-type alkali-added platinum-loaded alumina catalyst may be arranged in series or may be arranged in a mutually mixed manner.

[0060] In this way, the egg shell-type platinum-loaded alumina catalyst can be favorably used in the dehydrogenation reaction of hydrogenated aromatic, such as methylcyclohexane, used as a hydrogen energy carrier, and contributes to practical implementation of the hydrogen storage and transportation system according to the organic chemical hydride method. Besides, there is a possibility that the uniform-type platinum-loaded alumina catalyst can be widely applied to the existing catalytic reaction processes in which the platinum-loaded alumina catalyst is used, and the industrial applicability is very high.

[0061] Hereinafter, preferable embodiments of the present invention will be specifically described based on Examples and Comparative Examples.

[Carrier Preparation]

[0062] 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. The alumina carrier thus obtained had a BET surface area of 257 m.sup.2/g, a pore volume as measured by a mercury injection method of 0.66 cm.sup.3/g, an average pore diameter of 9.3 nm, and a sharp pore distribution in which most pores were concentrated around the average pore diameter. The volume occupied by pores with a pore diameter of 7-13 nm was 85% or more of the total pore volume, and from this result, the obtained porous γ-alumina carrier satisfied the requirements of the surface area of 150 m.sup.2/g or more, the pore volume of 0.40 cm.sup.3/g or more, the average pore diameter of 40 to 300 Å, and the pores having a pore diameter in a range of ±30 Å from the average pore diameter occupying 60% or more of the total pore volume.

Comparative Example 1 (Catalyst No. 1)

[0063] For the purpose of comparison with the Examples, an egg shell-type platinum-loaded alumina catalyst (catalyst No. 1) according to Comparative Example 1 was produced. 40 mL of chloroplatinic acid aqueous solution with a concentration of 0.026 mol/L, which was prepared so that the pH value was 2.0, was added to 20 g of the porous γ-alumina carrier prepared as mentioned above, and this was left for 3 hours for impregnation before water was removed with an evaporator. Subsequently, the resultant was dried for 3 hours at 120° C. and then was calcined for 3 hours at 450° C. in a muffle furnace under air flow, whereby an egg shell-type platinum-loaded alumina catalyst on which 1 wt % of platinum was loaded (catalyst No. 1) was prepared.

Comparative Example 2 (Catalyst No. 2)

[0064] 40 mL of sodium (Na) nitrate aqueous solution with a concentration of 0.085 mol/L was added to 20 g of the egg shell-type platinum-loaded alumina catalyst prepared and obtained similarly to Comparative Example 1, and this was left for 3 hours for impregnation before water was removed with an evaporator. Subsequently, the resultant was dried for 3 hours at 120° C. and then was calcined for 3 hours at 450° C. in muffle furnace under air flow, whereby, an egg shell-type alkali-added platinum-loaded alumina catalyst on which 0.8 wt % of sodium (Na) and 1 wt % of platinum were loaded (catalyst No. 2) was obtained. The egg shell-type alkali-added platinum-loaded alumina catalyst according to Comparative Example 2 corresponds to the catalyst described in the aforementioned Patent Document 1.

Comparative Example 3 (Catalyst No. 3)

[0065] 40 mL of ammonium sulfate aqueous solution with a concentration of 0.16 mol/L was added to 20 g of the porous γ-alumina carrier prepared according to the aforementioned method, and this was left for 3 hours for impregnation before water was removed with an evaporator. Subsequently, the resultant was dried for 3 hours at 120° C. and then was calcined for 3 hours at 500° C. in a muffle furnace under air flow, whereby an alumina carrier containing sulfur was obtained. 40 mL of chloroplatinic acid aqueous solution with a concentration of 0.026 mol/L, which was prepared so that pH was 2.0, was added to 20 g of the alumina carrier containing sulfur thus prepared, and after impregnation for making the loading amount of platinum after calcination be 1.0 wt %, moisture was removed with an evaporator. Subsequently, the resultant was dried for 3 hours at 120° C. and then was calcined for 3 hours at 450° C. in a muffle furnace under air flow, whereby a uniform-type sulfur-platinum-loaded alumina catalyst which contained 1.0 wt % of sulfur and on which 1.0 wt % of platinum was dispersed and loaded (catalyst No. 3) was obtained. This method conforms to the preparation method described in Example 3 of Patent Document 2.

Comparative Example 4 (Catalyst No. 4)

[0066] 20 g of alumina carrier containing sulfur prepared by the method same as in Comparative Example 3 was impregnated with 5.6 mL of dinitrodiamine platinum aqueous solution with a concentration of 0.18 mol/L so that the loading amount of platinum after calcination was 1.0 wt %, and thereafter, moisture was removed with an evaporator. Subsequently, the resultant was dried for 3 hours at 120° C. and then was calcined for 3 hours at 450° C. in a muffle furnace under air flow, whereby an egg shell-type sulfur-platinum-loaded alumina catalyst which contained 1.0 wt % of sulfur and on which 1.0 wt % of platinum was loaded in an egg shell manner was obtained. 40 mL of sodium nitrate (Na) aqueous solution with a concentration of 0.17 mol/L was added to 20 g of the egg shell-type sulfur-platinum-loaded alumina catalyst thus prepared, and this was left for 3 hours for impregnation before water was removed with an evaporator. Subsequently, the resultant was dried for 3 hours at 120° C. and then was calcined for 3 hours at 450° C. in a muffle furnace under air flow, whereby an egg shell-type alkali-added sulfur-platinum-loaded alumina catalyst on which 0.8 wt % of sodium (Na) and 1 wt % of platinum were loaded (catalyst No. 4) was obtained.

Example 1 (Catalyst No. 5)

[0067] 20 g of the porous γ-alumina carrier prepared by the method described in “Carrier Preparation” is impregnated with 33.2 mL of an aqueous solution obtained by adding oxalic acid to an ammonium metavanadate solution with a concentration of 0.12 mol/L in the same weight and dissolving oxalic acid therein, and this was left for 3 hours before water was removed with an evaporator. Subsequently, the resultant was dried for 3 hours at 120° C. and then was calcined for 3 hours at 500° C. in a muffle furnace under air flow, whereby an alumina carrier containing 1.2 wt % of vanadium (V) as the second component was obtained. Platinum was loaded on the vanadium-containing alumina carrier thus prepared by a method similar to Comparative Example 4 (Catalyst No. 4) using dinitrodiamine platinum aqueous solution, whereby an egg shell-type vanadium-added platinum-loaded alumina catalyst on which 1.2 wt % of vanadium and 1.0 wt % of platinum were loaded (catalyst No. 5) was obtained. [Example 2 (Catalyst No. 6)]

[0068] 20 of the porous γ-alumina carrier prepared by the method described in “Carrier Preparation” was impregnated with 32.0 mL of chromium nitrate aqueous solution with a concentration of 0.12 mol/L, and this was left for 3 hours before water was removed with an evaporator. Subsequently, the resultant was dried for 3 hours at 120° C. and then was calcined for 3 hours at 500° C. in a muffle furnace under air flow, whereby an alumina carrier containing 1.2 wt % of chromium (Cr) as the second component was obtained. Platinum was loaded on the chromium-containing alumina carrier thus prepared by a method similar to Comparative Example 4 (catalyst No. 4) using dinitrodiamine platinum aqueous solution, whereby an egg shell-type chromium-added platinum-loaded alumina catalyst on which 1.2 wt % of chromium and 1.0 wt % of platinum were loaded (catalyst No. 6) was obtained.

Example 3 (Catalyst No. 7)

[0069] 20 of the porous γ-alumina carrier prepared by the method described in “Carrier Preparation” is impregnated with 32.0 mL of ammonium molybdate aqueous solution with a concentration of 0.009 mol/L, and this was left for 3 hours before water was removed with an evaporator. Subsequently, the resultant was dried for 3 hours at 120° C. and then was calcined for 3 hours at 500° C. in a muffle furnace under air flow, whereby an alumina carrier containing 1.3 wt % of molybdenum (Mo) as the second component was obtained. Platinum was loaded on the molybdenum-containing alumina carrier thus prepared by a method similar to Comparative Example 4 (catalyst No. 4) using dinitrodiamine platinum aqueous solution, whereby an egg shell-type molybdenum-added platinum-loaded alumina catalyst on which 1.3 wt % of molybdenum and 1.0 wt % of platinum were loaded (catalyst No. 7) was obtained.

Example 4 (Catalyst No. 8)

[0070] 20 of the porous γ-alumina carrier prepared by the method described in “Carrier Preparation” was impregnated with 32.0 mL of ammonium dihydrogen phosphate aqueous solution with a concentration of 0.20 mol/L, and this was left for 3 hours before water was removed with an evaporator. Subsequently, the resultant was dried for 3 hours at 120° C. and then was calcined for 3 hours at 500° C. in a muffle furnace under air flow, whereby an alumina carrier containing 0.9 wt % of phosphorus (P) as the second component was obtained. Platinum was loaded on the phosphorus-containing alumina carrier thus prepared by a method similar to Comparative Example 4 (Catalyst No. 4) using dinitrodiamine platinum aqueous solution, whereby an egg shell-type phosphorus-added platinum-loaded alumina catalyst on which 0.9 wt % of phosphorus and 1.0 wt % of platinum were loaded (catalyst No. 8) was obtained.

Examples 5 and 6 (Catalyst Nos. 9 and 10)

[0071] By a method similar to Example 1 with varied concentrations of ammonium metavanadate aqueous solution, alumina carriers respectively containing 0.5 wt % and 2.0 wt % of vanadium (V) as the second component were prepared, and thereafter, platinum was loaded thereon in a similar way, whereby an egg shell-type vanadium-added platinum-loaded alumina catalyst on which 0.5 wt % of vanadium and 1.0 wt % of platinum were loaded (catalyst No. 9) and an egg shell-type vanadium-added platinum-loaded alumina catalyst on which 2.0 wt % of vanadium and 1.0 wt % of platinum were loaded (catalyst No. 10) were obtained.

Example 7 (Catalyst No. 11)

[0072] By a method similar to Example 1 with a varied concentration of ammonium metavanadate aqueous solution, an alumina carrier containing 0.5 wt % of vanadium (V) as the second component was prepared, and thereafter, the concentration of dinitrodiamine platinum aqueous solution was adjusted in a similar way, whereby an egg shell-type vanadium-added platinum-loaded alumina catalyst on which 0.5 wt % of vanadium and 0.5 wt % of platinum were loaded (catalyst No. 11) was obtained.

Examples 8-10 (Catalyst Nos. 12-14)

[0073] By a method similar to Example 2 with varied concentrations of chromium nitrate aqueous solution, alumina carriers respectively containing 0.5 wt %, 2.0 wt %, and 3.0 wt % of chromium (Cr) as the second component were prepared, and thereafter, platinum was loaded thereon in a similar way, whereby an egg shell-type chromium-added platinum-loaded alumina catalyst on which 0.5 wt % of chromium and 1.0 wt % of platinum were loaded (catalyst No. 12), an egg shell-type chromium-added platinum-loaded alumina catalyst on which 2.0 wt % of chromium and 1.0 wt % of platinum were loaded (catalyst No. 13), and an egg shell-type chromium-added platinum-loaded alumina catalyst on which 3.0 wt % of chromium and 1.0 wt % of platinum were loaded (catalyst No. 14) were obtained.

Examples 11 and 12 (Catalyst Nos. 15 and 16)

[0074] By a method similar to Example 3 with varied concentrations of ammonium molybdate aqueous solution, alumina carriers respectively containing 0.5 wt % and 2.0 wt % of molybdenum (Mo) as the second component were prepared, and thereafter, platinum was loaded thereon in a similar way, whereby an egg shell-type molybdenum-added platinum-loaded alumina catalyst on which 0.5 wt % of molybdenum and 1.0 wt % of platinum were loaded (catalyst No. 15) and an egg shell-type molybdenum-added platinum-loaded alumina catalyst on which 2.0 wt % of molybdenum and 1.0 wt % of platinum were loaded (catalyst No. 16) were obtained.

(Accelerated Reaction Test)

[0075] Next, a reaction test was performed using the aforementioned Comparative Examples 1 to 4 (Catalyst Nos. 1 to 4) and Examples 1 to 12 (Catalyst Nos. 5 to 16). The reaction test was performed under accelerated condition so that differences in performance were obtained in a relatively short time. 1.3 g of each catalyst was diluted with 11.7 g of α-alumina beads and was charged in a lengthwise central part of 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 protective tube for a thermocouple whose outer dimension was ⅛ inch in the center of the cross section of the reaction tube. Spherical α-alumina beads with a diameter of 1 mm were placed on the upper side of the catalyst as a preheating layer. Thereafter, the temperature of the catalyst layer was raised to 380° C., and pre-treatment reduction was carried out for 15 hours in a hydrogen stream. After the pre-treatment reduction finished, the catalyst layer inlet temperature was set to 400° C., the catalyst layer outlet temperature was set to 410° C., the pressure was set to 0.3 MPa, the hydrogen gas supplied for the pre-treatment reduction was stopped, and methylcyclohexane (MCH) gas evaporated by a heater was supplied to the reactor at a flow rate of 2.9 L/h (LHSV: 8 h.sup.−1). A cooler for cooling the gas exiting from the reactor was provided at the outlet of the reaction tube, and the resultant was collected in a stainless steel container and was separated into a liquid product such as liquefied toluene (TOL) and gas such as hydrogen gas. Composition analysis was performed separately for the collected liquid product and gas by gas chromatography, and the MCH conversion rate (%) and the TOL selectivity (%) from the reaction start to 140 hours later were calculated. Also, the catalyst after the reaction test was taken out, and an amount of carbon production, which is a cause for catalyst deterioration, was measured with a carbon/sulfur analyzer.

(Catalyst Life Test)

[0076] Next, by using the aforementioned Comparative Example 3 (catalyst No. 3) and Example 1 (Catalyst No. 5), a long time reaction test was carried out as follows. 8.5 g of each catalyst was diluted with 129 g of spherical α-alumina beads with an outer diameter of 5 mm and charged in a lengthwise central part of a stainless steel reaction tube which had an inside diameter of 21.2 mm and a length of 816 mm and which was equipped with a protection tube for a thermocouple whose outer dimension was ¼ inch in the center of the cross section of the reaction tube. Spherical α-alumina beads with an outer diameter of 1 mm were placed on the upper side of the catalyst as a preheating layer. The temperature of the catalyst layer was set to 380° C., and pre-treatment reduction was carried out for 15 hours in a hydrogen stream. After the pre-treatment reduction finished, the catalyst layer inlet temperature was set to 280° C., the catalyst layer outlet temperature was set to 380° C., the reaction pressure was set to 0.55 MPa, and MCH gas was supplied to the reactor at a flow rate of 2.8 L/h (LHSV: 2.6 h.sup.−1). A cooler for cooling the gas exiting from the reactor was provided at the outlet of the reaction tube, and the resultant was collected in a stainless steel container and was separated into a liquid product such as liquefied toluene and gas such as hydrogen gas. Composition analysis was performed separately for the collected liquid product and gas by gas chromatography, and the MCH conversion rate (%) and the TOL selectivity (%) from the reaction start to 1400 hours later were calculated.

[0077] The result of the aforementioned accelerated reaction test is shown in Tables 1 to 4, and the result of the catalyst life test is shown in Table 5.

TABLE-US-00001 TABLE 1 accelerated test comparison between second component elements after 20 hours after 140 hours second component MCH MCH amount of loading conversion TOL conversion TOL carbon catalyst amount Pt rate selectivity rate selectivity production No. element (wt %) (wt %) (%) (%) (%) (%) (wt %) 1 Comparative none — 1.0 95.7 99.3 90.4 99.6 2.6 Example 1 2 Comparative Na 0.8 1.0 94.5 99.6 88.0 99.8 1.5 Example 2 3 Comparative S 1.0 1.0 98.7 99.8 95.0 99.8 2.6 Example 3 4 Comparative S—Na 1.0-0.8 1.0 97.3 98.0 93.9 97.9 0.5 Example 4 (ES-Na) 5 Example 1 V 1.2 1.0 99.5 99.9 98.4 99.9 0.7 6 Example 2 Cr 1.2 1.0 99.4 99.9 98.1 99.9 1.4 7 Example 3 Mo 1.3 1.0 98.5 99.9 96.2 99.9 0.8 8 Example 4 P 0.9 1.0 98.8 99.7 97.0 99.9 1.2

[0078] From Table 1, it can be seen that compared to the egg shell-type platinum-loaded alumina catalyst of Comparative Example 1 (Catalyst No. 1) in which platinum was dispersed and loaded on only the outer shell part of the carrier and the egg shell-type alkali-added platinum-loaded alumina catalyst of Comparative Example 2 (Catalyst No. 2), the uniform-type sulfur-platinum-loaded alumina catalyst of Comparative Example 3 (Catalyst No. 3) in which sulfur was dispersed and loaded over the entirety of the alumina carrier and platinum was dispersed and loaded over the entirety of the alumina carrier demonstrated a high MCH conversion rate and a high TOL selectivity both at an initial stage of the accelerated reaction test and after 140 hours of reaction (the MCH conversion rate was 98.7% and 95.0%, respectively), and thus, is excellent in the catalyst stability and selectivity.

[0079] As described above, the uniform-type sulfur-platinum-loaded alumina catalyst of Comparative Example 3 demonstrates excellent catalyst performance, but the amount of carbon production after the reaction test was 2.6 wt %, which is greater than that of the egg shell-type alkali-added platinum-loaded alumina catalyst of Comparative Example 2 (Catalyst No. 2). From this result, it is inferred that in the catalyst of Comparative Example 3, dispersity is improved due to uniform dispersion of platinum, which is the catalyst component, over the carrier, and this provides numerous active sites effective for reaction, whereby even though the amount of carbon precipitation is increased, active sites effective for reaction are still held.

[0080] Similarly, from Table 1, it can be seen that in each of Examples 1 to 4 (Example 1: vanadium, Example 2: chromium, Example 3: molybdenum, Example 4: phosphorus), the MCH conversion rate 20 hours after the reaction start was equivalent to or higher than that of Comparative Example 3, and the MCH conversion rate 140 hours after was maintained to a value equal to or higher than that of Comparative Example 3, and thus, the catalyst was better in stability compared to Comparative Example 3. Also, the TOL selectivity was 99.9%, which was better than that of Comparative Example 3, and the amount of carbon production after the reaction test was 0.7 to 1.4%, which was about ⅓ to ½ from 2.6 wt % of Comparative Example 3. The improvement of TOL selectivity was 0.1% numerically, but since the amount of impurities produced is calculated according to the formula below, the improvement of the TOL selectivity from 99.8% to 99.9% suppresses the amount of impurities produced to about a half.

Amount of impurities produced=Supply amount of MCH×MCH conversion rate/100×(100−TOL selectivity)/100

[0081] The egg shell-type platinum-loaded alumina catalysts of Examples 1 to 4 exhibited a high MCH conversion rate and a high TOL selectivity even compared to the egg shell-type platinum-loaded alumina catalyst of Comparative Example 4 in which sulfur and sodium were added. From these, it can be seen that when the additive to the egg shell-type platinum-loaded alumina catalyst is vanadium, chromium, molybdenum, or phosphorus, the MCH conversion rate and the TOL selectivity are improved better than when the additive is sodium, which is an alkali metal.

TABLE-US-00002 TABLE 2 accelerated test effect of the loading amount of Vd, reduction of amount of Pt after 20 hours after 140 hours second component MCH MCH amount of loading conversion TOL conversion TOL carbon catalyst amount Pt rate selectivity rate selectivity production No. element (wt %) (wt %) (%) (%) (%) (%) (wt %) 5 Example 1 V 1.2 1.0 99.5 99.9 98.4 99.9 0.7 9 Example 5 V 0.5 1.0 99.4 99.9 98.2 99.9 0.8 10 Example 6 V 2.0 1.0 96.9 99.9 96.6 99.9 0.5 11 Example 7 V 0.5 0.5 99.5 99.9 97.0 99.9 0.5

[0082] From Table 2 for assessing the effect of the loading amount of vanadium, it can be seen that when the loading amount of vanadium is increased to about 2.0 wt % (Example 6), the MCH conversion rate starts to decrease. On the other hand, regarding the amount of carbon production, the results show that there is no significant influence so long as the loading amount of vanadium is 0.5 wt % (Example 5) or greater.

[0083] Also, from Table 2, it can be seen that in Example 7 in which the weight ratio of vanadium and platinum was maintained to 1:1 and the amount of platinum was reduced to 0.5 wt %, the MCH conversion rates after 20 hours and after 140 hours were higher than those of Comparative Example 3 (see Table 1). This indicates that by adopting an egg shell-type platinum-loaded alumina catalyst to which the second metal component is added, it is possible to increase the amount of platinum present on the outer periphery of the catalyst which is effective for the reaction and thereby to decrease the loading amount of expensive platinum.

TABLE-US-00003 TABLE 3 accelerated test effect of the loading amount of Cr after 20 hours after 140 hours second component MCH MCH amount of loading conversion TOL conversion TOL carbon catalyst amount Pt rate selectivity rate selectivity production No. element (wt %) (wt %) (%) (%) (%) (%) (wt %) 6 Example 2 Cr 1.2 1.0 99.4 99.9 98.1 99.9 1.4 12 Example 8 Cr 0.5 1.0 97.7 99.8 95.5 99.8 1.2 13 Example 9 Cr 2.0 1.0 98.7 99.9 97.0 99.9 1.0 14 Example 10 Cr 3.0 1.0 96.0 99.9 95.1 99.9 0.8

[0084] From Table 3 for assessing the effect of the loading amount of chromium, it can be seen that when the loading amount of chromium is increased to about 3.0 wt %, the MCH conversion rate starts to decrease. In the case of chromium, with the loading amount of 0.5 wt %, the TOL selectivity is approximately equivalent to that of Comparative Example 3, and the loading to 1.0 wt % or greater is effective for increasing the selectivity. On the other hand, regarding the amount of carbon production, the results show that there is no significant influence so long as the loading amount of chromium is 0.5 wt % or greater.

TABLE-US-00004 TABLE 4 accelerated test effect of the loading amount of Mo after 20 hours after 140 hours second component MCH MCH amount of loading conversion TOL conversion TOL carbon catalyst amount Pt rate selectivity rate selectivity production No. element (wt %) (wt %) (%) (%) (%) (%) (wt %) 7 Example 3 Mo 1.3 1.0 98.5 99.9 96.2 99.9 0.8 15 Example 11 Mo 0.5 1.0 97.7 99.9 94.5 99.9 0.8 16 Example 12 Mo 2.0 1.0 97.2 99.9 90.4 99.8 0.7

[0085] From Table 4 for assessing the effect of the loading amount of molybdenum, it can be seen that in the cases where the loading amount of molybdenum was 0.5 wt % and 2.0 wt %, the MCH conversion rate was slightly low compared to the case where the loading amount of molybdenum was 1.3 wt %, and that the most favorable MCH conversion rate and stability were demonstrated in the case where, the loading amount of molybdenum was 1.0 wt % or greater.

[0086] Table 5 shows a result of the catalyst life test performed on Example 1 (Catalyst No. 5, vanadium 1.8 wt %), which from the accelerated test results of Examples 1 to 12, demonstrated an MCH conversion rate that was relatively high and changed stably and an amount of carbon production that was relatively small, and Comparative Example 3.

TABLE-US-00005 TABLE 5 life test comparison between second component elements after 50 hours after 1200 hours second component MCH MCH amount of loading conversion TOL conversion TOL carbon catalyst amount Pt rate selectivity rate selectivity production No. element (wt %) (wt %) (%) (%) (%) (%) (wt %) 3 Comparative S 1.0 1.0 97.5 99.6 96.7 99.7 2.7 Example 3 5 Example 1 V 1.2 1.0 97.1 99.9 96.7 99.9 1.1

[0087] From Table 5, in the egg shell-type platinum-loaded alumina catalyst of Example 1 (Catalyst No. 5) to which the second component was added, the MCH conversion rate decreased by only 0.4% over the period from 50 hours after the reaction start to 1200 hours after the reaction start, while in the uniform-type platinum-loaded alumina catalyst of Comparative Example 3 (Catalyst No. 3), the MCH conversion rate decreased by 0.8%, and thus, the egg shell-type second component-added platinum-loaded alumina catalyst is expected to have a long catalyst life. Also, regarding the TOL selectivity, the egg shell-type second component-added platinum-loaded alumina catalyst maintained 99.9% over the period from 50 hours after the reaction start to 1200 hours after the reaction start, which is higher than the TOL selectivity of the uniform-type platinum-loaded alumina catalyst of Comparative Example 3 (Catalyst No. 3), and thus, it can be seen that the egg shell-type second component-added platinum-loaded alumina catalyst is a catalyst that produces a small amount of impurities. In addition, the amount of carbon production after 1200 hours of reaction test was 1.1% in Example 1, which is smaller than 2.7% in Comparative Example 3, and thus, it is indicated that by suppressing the amount of carbon production, an effect of enhancing the stability of the catalyst can be obtained.

INDUSTRIAL APPLICABILITY

[0088] The egg shell-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 by organic chemical hydride method. Besides, there is a possibility that the alkali-added uniform-type platinum-loaded alumina catalyst according to the present invention can be widely applied to 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

[0089] 1 carrier [0090] 2 metal loading part