Patent Description:
The hydrotreating process of heavy hydrocarbon oils such as residual oils containing metal contaminants is a process in which a hydrocarbon oil is subjected to hydrodesulfurization and hydrodemetallation under high-temperature and high-pressure reaction conditions in a stream of hydrogen. The reactions are performed in a fixed bed reaction column charged with a demetallation catalyst having high demetallation selectivity, and a desulfurization catalyst having high desulfurization selectivity.

As the trend for using heavier feedstock oils, and the demand for reducing the load on the fluid catalytic cracking process performed after the hydrotreatment process continue to rise, the catalysts for hydrotreating process are required to satisfy high desulfurization performance and high catalyst stability. In order to reduce cracking and powderization during regeneration of a used catalyst, the catalysts should also desirably have sufficient strength and abrasion strength even before use.

PTL <NUM> describes a technique whereby a calcium compound is contained in a support primarily made of alumina to improve demetallation performance, and to reduce cracking and powderization even in regenerating a catalyst. Calcium has strong affinity to vanadium, and facilitates demetallation reaction. Calcium also allows vanadium to be immobilized in a catalyst, and improves regeneration performance. However, when a calcium compound having a small surface area is added, the surface area of the catalyst becomes smaller, and improvements are needed for desulfurization performance and desulfurization stability.

PTL <NUM> discloses a technique for making a wider pore distribution for a hydrotreating catalyst using an alumina-phosphorus support. The technique is intended to improve demetallation performance and deasphaltene performance. The technique is desirable in terms of demetallation reactivity of macromolecules such as asphaltenes, but needs improvements in desulfurization performance and desulfurization stability.

An object of the invention is to provide a hydrotreating catalyst for hydrocarbon oil having high desulfurization activity, and high abrasion strength and high compressive strength, and a process for producing such a hydrotreating catalyst. The invention is also intended to provide a hydrotreating method for hydrocarbon oil whereby sulfur can be removed from hydrocarbon oil at high efficiency.

A first invention is a hydrotreating catalyst for hydrocarbon oil using an oxide support containing aluminum and phosphorus,.

The first invention may have the following features.

A second invention is a process for producing a hydrotreating catalyst for hydrocarbon oil using an oxide support containing aluminum and phosphorus,
the process comprising:.

A third invention is a method for hydrotreating a hydrocarbon oil, the method comprising contacting the hydrocarbon oil to the hydrotreating catalyst of claim <NUM> at a temperature of <NUM> to <NUM>, a pressure of <NUM> to <NUM> MPa, and a liquid hourly space velocity of <NUM> to <NUM> hr-<NUM> in the presence of hydrogen.

The hydrotreating catalyst for hydrocarbon oil using an oxide support containing aluminum and phosphorus (in the following simply referred to as an "alumina-phosphorus support") according to the invention has two maximal peaks in a pore diameter range of <NUM> to <NUM> in a log differential pore volume distribution measured by a mercury intrusion method. Accordingly, particle mixing occurs between relatively larger pores and relatively smaller pores. Specifically, smaller particles enter the space between larger particles, and provide high abrasion strength and high compressive strength for the support.

Further, because the absorbance ratio Sb/Sa between the absorbance Sb of a basic OH group and the absorbance Sa of an acidic OH group is in a range of <NUM> to <NUM> as measured by using a transmission Fourier transformation infrared spectrophotometer, the hydroactive metals loaded on the support can have high dispersibility, and high desulfurization performance.

The invention is a hydrotreating catalyst for hydrocarbon oil using an alumina-phosphorus support (hereinafter, referred to as "present catalyst"). The following describes an embodiment of the present catalyst, and an embodiment of a process for producing the present catalyst.

The alumina-phosphorus support constituting the present catalyst contains <NUM> to <NUM> mass% of phosphorus in terms of a P<NUM>O<NUM> concentration with respect to the total support amount. The phosphorus content is more preferably <NUM> to <NUM> mass%. The catalyst strength may become weaker when the phosphorus content in the support is less than <NUM> mass%. When the phosphorus content exceeds <NUM> mass%, the pore volume in a pore diameter range of <NUM> to <NUM>,<NUM> becomes excessively large, and the catalyst strength may become weaker. This may also lead to reduced catalyst bulk density, and poor catalyst performance. The alumina-phosphorus support may contain only oxides of alumina and phosphorus, or may additionally contain inorganic oxides of silica, boria, titania, zirconia, and manganese, for example.

In the present catalyst, metals in Group 6A and Group <NUM> of the periodic table are loaded as hydroactive metals on the support. The hydroactive metal is loaded in an amount of preferably <NUM> to <NUM> mass% in terms of an oxide with respect to the total catalyst amount. With the hydroactive metal loaded in an amount of <NUM> mass% or more, the invention can more effectively show effects. The hydroactive metal is loaded in an amount of preferably <NUM> mass% or less because it enables maintaining demetallation performance (demetallation selectivity) and catalytic activity stability, and reducing the production cost. Preferred as the Group 6A metals are chromium, molybdenum, and tungsten. Preferred as the Group <NUM> metals are iron, nickel, and cobalt.

The present catalyst has a specific surface area of <NUM><NUM>/g or more. When the specific surface area is less than <NUM><NUM>/g, the desulfurization reaction rate tends to decrease, though the effect on demetallation performance remains small in this range of specific surface area. As used herein, "specific surface area" is a measured value by the BET method.

The present catalyst has a total pore volume of <NUM> to <NUM>/g as measured by a mercury intrusion method. When the total pore volume is less than <NUM>/g, desulfurization performance tends to decrease due to blocking of pores by metal. The catalyst strength tends to decrease when the total pore volume is larger than <NUM>/g. As used herein, "total pore volume" means a pore volume in a pore diameter range of <NUM> to <NUM>,<NUM> (the upper and lower values of analyzed raw data). The pore diameter is a calculated value based on a mercury surface tension of <NUM> dyne/cm, and a contact angle of <NUM>°.

The present catalyst has two maximal peaks in a pore diameter range of <NUM> to <NUM> in a log differential pore volume distribution measured by a mercury intrusion method. Demetallation performance becomes poor when either or both of these maximal peaks are in a pore diameter range below <NUM>. Desulfurization performance tends to deteriorate when either or both of the two maximal peaks are in a pore diameter range above <NUM>. With the two maximal peaks occurring in a pore diameter range of <NUM> to <NUM>, particle mixing occurs between relatively larger pores and relatively smaller pores. Specifically, smaller particles enter in the space between larger particles, and provide high abrasion strength and high compressive strength for the support.

<FIG> represents an exemplary log differential pore volume distribution created for the present catalyst. The horizontal axis represents pore diameter, and the vertical axis represents values obtained by dividing the differential pore volume dV by the logarithmic differential value d (logD) of pore diameter. <FIG> corresponds to Example <NUM> to be described later.

The present catalyst has an abrasion strength of <NUM>% or less. When the abrasion strength of the catalyst exceeds <NUM>%, cracking and powderization tend to occur also in regeneration of a used catalyst. The abrasion strength is a measured value based on ASTM D4058-<NUM>.

The present catalyst has a compressive strength of <NUM> N/mm or more. When the compressive strength of the catalyst is less than <NUM> N/mm, the catalyst tends to break when being charged, and drifting or pressure loss may occur during reaction. Compressive strength is also called crush strength. In the invention, the compressive strength is a measured value using a Kiya hardness meter.

The support of present catalyst has an absorbance ratio Sb/Sa of <NUM> to <NUM>, wherein Sb is the absorbance Sb of the spectral peak in a wavenumber range of <NUM>,<NUM> to <NUM>,<NUM>-<NUM> corresponding to a basic OH group, and Sa is the absorbance Sa of the spectral peak in a wavenumber range of <NUM>, <NUM> to <NUM>, <NUM>-<NUM> corresponding to an acidic OH group as measured by using a transmission Fourier transformation infrared spectrophotometer. The absorbance ratio Sb/Sa is more preferably <NUM> to <NUM>. As is known, active metals show different dispersibility depending on the characteristics of the alumina support surface. By optimizing the ratio of an acidic OH group and a basic OH group as above for the OH groups on the support surface, and from the fact that the support is an alumina-phosphorus support, it is possible to improve the dispersibility of the hydroactive metals, and desulfurization performance. <FIG> represents an example of a photoabsorption spectrum of the support of the present catalyst, including a wavenumber range of <NUM>,<NUM> to <NUM>,<NUM>-<NUM> corresponding to an acidic OH group, and a wavenumber range of <NUM>,<NUM> to <NUM>,<NUM>-<NUM> corresponding to a basic OH group. (Example <NUM>: the phosphorus content in the support is <NUM> mass% in terms of a P<NUM>O<NUM> concentration. ) In this example, the absorbance Sa of the spectral peak corresponding to an acidic OH group is <NUM>, and the absorbance Sb of the spectral peak corresponding to a basic OH group is <NUM>. The absorbance ratio Sb/Sa is <NUM> accordingly.

The specific procedures of absorbance measurement are described below. A sample (<NUM>) is charged into a molding container (inner diameter φ of <NUM>), and is molded into a thin disc shape by being compressed under an applied pressure of <NUM> ton/cm<NUM> (<NUM>,<NUM> N/cm<NUM>). The molded body is maintained at <NUM> for <NUM> hours in a vacuum of <NUM> × <NUM>-<NUM> Pa or less, and measured for absorbance after being cooled to room temperature.

Specifically, the absorbance was measured with a TGS detector at a resolution of <NUM>-<NUM> for <NUM> runs, and the baseline was corrected for a wavenumber range of <NUM>,<NUM> to <NUM>,<NUM>-<NUM>, followed by correction with the specific surface area. The absorbance was converted to a value per unit surface area, and a value per unit mass. <MAT> <MAT>.

A preferred embodiment for producing the present catalyst is described below.

An acidic aluminum salt is added to weighed water to prepare an acidic aluminum aqueous solution that contains, for example, <NUM> to <NUM> mass% of Al<NUM>O<NUM>, and has a pH of <NUM> to <NUM>. The acidic aluminum aqueous solution is then heated to a liquid temperature of, for example, <NUM> to <NUM> while being stirred. The acidic aluminum salt is a water-soluble salt, and may be, for example, aluminum sulfate, aluminum chloride, aluminum acetate, or aluminum nitrate. Preferably, the aqueous solution contains <NUM> to <NUM> mass% of an acidic aluminum salt in terms of Al<NUM>O<NUM>.

While stirring the acidic aluminum aqueous solution, a basic aluminum aqueous solution is added thereto for, for example, <NUM> to <NUM> minutes to make the pH <NUM> to <NUM>, and obtain an alumina hydrate. The alumina hydrate is then washed with, for example, <NUM> to <NUM> purified water, and impurity by-product salts such as sodium, and sulfate radicals are removed to obtain a cake-like alumina hydrate (A). Examples of the basic aluminum salt include sodium aluminate, and potassium aluminate. Preferably, the aqueous solution contains <NUM> to <NUM> mass% of a basic aluminum salt in terms of Al<NUM>O<NUM>.

A basic aluminum salt is added to weighed water to prepare a basic aluminum aqueous solution that contains, for example, <NUM> to <NUM> mass% of Al<NUM>O<NUM>, and has a pH of <NUM> to <NUM>. The basic aluminum aqueous solution is then heated to a liquid temperature of, for example, <NUM> to <NUM> while being stirred.

While stirring the basic aluminum aqueous solution, an acidic aluminum aqueous solution is added thereto for, for example, <NUM> to <NUM> minutes to make the pH <NUM> to <NUM>, and obtain an alumina hydrate. The alumina hydrate is then washed with, for example, <NUM> to <NUM> purified water, and impurity by-product salts such as sodium salts, and sulfates are removed to obtain a cake-like alumina hydrate (B). Examples of the basic aluminum salt include the same chemicals exemplified in the first step. Preferably, the aqueous solution contains <NUM> to <NUM> mass% of a basic aluminum salt in terms of Al<NUM>O<NUM>. Examples of the acidic aluminum salt include the same chemicals exemplified in the first step. Preferably, the aqueous solution contains <NUM> to <NUM> mass% of an acidic aluminum salt in terms of Al<NUM>O<NUM>.

Purified water is added, and mixed with each of the cake-like alumina hydrates (A) and (B), and these are mixed to obtain a slurry-like alumina hydrate. Phosphorus is then added to the slurry-like alumina hydrate to obtain an alumina-phosphorus hydrate. Phosphorus is added to make the phosphorus content, for example, <NUM> to <NUM> mass% in the support in terms of a P<NUM>O<NUM> concentration. The phosphorus source may be a phosphoric acid compound, for example, such as phosphoric acid, phosphorous acid, ammonia phosphate, potassium phosphate, and sodium phosphate. The mixture ratio of alumina hydrate (A) and alumina hydrate (B) is A/B > <NUM>. When A/B < <NUM>, only a single maximal peak occurs in a pore diameter range of <NUM> to <NUM>, and abrasion strength and compressive strength deteriorate.

The alumina-phosphorus hydrate obtained in the third step is aged in an aging tank equipped with a reflux condenser at <NUM> or more, preferably <NUM> to <NUM>, for, for example <NUM> to <NUM> hours. The aged product is, for example, kneaded under heat to obtain a moldable kneaded product using a common means, and molded into the desired shape by, for example, extrusion molding. After being dried, the product is calcined at <NUM> to <NUM> for <NUM> to <NUM> hours to obtain an alumina-phosphorus support.

The alumina-phosphorus support can then be used to produce a hydrotreating catalyst of the invention by loading a metal selected from Group 6A of the periodic table, and a metal selected from Group <NUM> of the periodic table, using a common means. Examples of the feedstock of such metals include metallic compounds such as nickel nitrate, nickel carbonate, cobalt nitrate, cobalt carbonate, molybdenum trioxide, ammonium molybdate, and ammonium paratungstate. The metals are loaded on the support using known methods, such as an impregnation method, and an immersion method. The support with the loaded metals is calcined at typically <NUM> to <NUM> for <NUM> to <NUM> hours to obtain a hydrotreating catalyst of the invention.

The catalyst having two maximal peaks in a pore diameter range of <NUM> to <NUM> in a log differential pore volume distribution can be obtained by using the support obtained by mixing the alumina hydrate (A) obtained by adding a basic aqueous aluminum salt solution to an acidic aqueous aluminum salt solution, and the alumina hydrate (B) obtained by adding an acidic aqueous aluminum salt solution to a basic aqueous aluminum salt solution, in the manner described in the first to third steps above.

The specific surface area, and the total pore volume of the present catalyst also can be controlled by varying the amount of the phosphorus added.

The hydrotreating catalyst of the invention has use in a hydrotreatment of heavy hydrocarbon oils such as residual oils containing metal contaminants such as vanadium, and nickel, and may be produced by using existing hydrotreatment devices, and the procedures used for these devices. As an example of such procedures, a heavy hydrocarbon oil is contacted to the hydrotreating catalyst of the invention at a temperature of <NUM> to <NUM>, a pressure of <NUM> to <NUM> MPa, and a liquid hourly space velocity of <NUM> to <NUM> hr-<NUM> in the presence of hydrogen.

Production of the present catalyst is simple and highly productive, and has a cost advantage.

The invention is described below in greater detail using Examples. The invention, however, is not limited by the following.

Purified water (<NUM>) was filled into a tank equipped with a circulation line having two chemical inlets. An acidic aqueous aluminum salt solution, specifically <NUM> of an aluminum sulfate aqueous solution (<NUM> mass% in terms of Al<NUM>O<NUM>) was added while being stirred, and the mixture was heated to <NUM>, and circulated. Here, the alumina aqueous solution (A1) had a pH of <NUM>. Thereafter, a basic aqueous aluminum salt solution, specifically <NUM> of a sodium aluminate aqueous solution (<NUM> mass% in terms of Al<NUM>O<NUM>) was added to the alumina aqueous solution (A1) for <NUM> minutes at the maintained temperature of <NUM> while being stirred and circulated, and an alumina hydrate (A) was obtained. The mixture had a pH of <NUM>. The alumina hydrate (A) was then washed with <NUM> purified water, and impurities such as sodium, and sulfate radicals were removed. Purified water was added to the washed cake to make the Al<NUM>O<NUM> concentration <NUM> mass%, and the solution was aged at <NUM> for <NUM> hours in an aging tank equipped with a reflux condenser to obtain a cake-like alumina hydrate (A).

Separately, purified water (<NUM>) was filled into a tank equipped with a steam jacket, and a basic aqueous aluminum salt solution, specifically <NUM> of a sodium aluminate aqueous solution (<NUM> mass% in terms of Al<NUM>O<NUM>) was added while being stirred. The mixture was then heated to <NUM>, and circulated. Here, the alumina aqueous solution (B1) had a pH of <NUM>. Thereafter, an acidic aqueous aluminum salt solution, specifically <NUM> of an aluminum sulfate aqueous solution (<NUM> mass% in terms of Al<NUM>O<NUM>) was added at a constant rate (for <NUM> minutes) with a roller pump until the pH of the mixed aqueous solution became <NUM>. The washed cake-like slurry was then diluted with ion-exchange water to make the Al<NUM>O<NUM> concentration <NUM> mass%. After dilution, the pH was brought to <NUM> with <NUM> mass% ammonia water. The product was then aged at <NUM> for <NUM> hours in an aging tank equipped with a reflux condenser to obtain an alumina hydrate (B).

The cake-like alumina hydrates (A) and (B), <NUM> each in terms of an Al<NUM>O<NUM> oxide, were mixed, and purified water was added to make the Al<NUM>O<NUM> concentration <NUM> mass%. Thereafter, <NUM> of phosphoric acid (<NUM> mass% in terms of P<NUM>O<NUM>) was added to the mixture of the alumina hydrates (A) and (B). The mixture was then stirred for <NUM> hour to obtain an alumina-phosphorus hydrate. After being stirred, the slurry was dehydrated, and concentrated and kneaded until the moisture content reached a predetermined level, using a twin-arm kneader equipped with a steam jacket. The knead product was then extrusion molded into a <NUM>-mm four-leaf columnar shape using an extrusion molding machine. The alumina molded product was dried at <NUM> for <NUM> hours, and calcined at <NUM> for <NUM> hours to obtain an alumina-phosphorus support a. The support a contained <NUM> mass% of phosphorus in terms of P<NUM>O<NUM>, and <NUM> mass% of aluminum in terms of Al<NUM>O<NUM> (the contents are with respect to the total support amount).

A molybdenum oxide (<NUM>), and a nickel carbonate (<NUM>) were suspended in <NUM> of ion-exchange water, and the suspension was superheated at <NUM> for <NUM> hours after an appropriate reflux process performed to prevent liquid volume reduction. Thereafter, <NUM> of citric acid was added, and dissolved to produce an impregnation solution. The impregnation solution was sprayed, and impregnated in <NUM> of support a, and the support a was dried at <NUM>, and calcined in an electric furnace at <NUM> for <NUM> hour to obtain a hydrotreating catalyst (hereinafter, also referred to simply as "catalyst") A. The metallic components of the catalyst A were <NUM> mass% MoOs (with respect to the total catalyst amount), and <NUM> mass% NiO (with respect to the total catalyst amount). The properties of the catalyst A are shown in Table <NUM>. The compressive strength was measured using a Kiya hardness meter (Fujiwara Scientific Company Co. The abrasion strength values are based on ASTM D4058-<NUM>. <FIG> shows the log differential pore volume distribution of catalyst A measured by a mercury intrusion method. <FIG> shows the result of the measurement performed for support a using a transmission Fourier transformation infrared spectrophotometer (FT-IR-<NUM>, available from JASCO Corporation).

An alumina-phosphorus support b was obtained in the same manner as in Example <NUM>, except that <NUM> of phosphoric acid was added. The support b contained <NUM> mass% of phosphorus in terms of P<NUM>O<NUM>, and <NUM> mass% of aluminum in terms of Al<NUM>O<NUM> (the contents are with respect to the total support amount). Catalyst B was obtained using support b, in the same manner as in Example <NUM>. The metallic components of catalyst B were <NUM> mass% MoOs (with respect to the total catalyst amount), and <NUM> mass% NiO (with respect to the total catalyst amount). The properties of catalyst B are shown in Table <NUM>.

An alumina-phosphorus support c was obtained in the same manner as in Example <NUM>, except that <NUM> of alumina hydrate (A) in terms of an Al<NUM>O<NUM> oxide, and <NUM> of alumina hydrate (B) in terms of an Al<NUM>O<NUM> oxide were mixed. The support c contained <NUM> mass% of phosphorus in terms of P<NUM>O<NUM>, and <NUM> mass% of aluminum in terms of Al<NUM>O<NUM> (the contents are with respect to the total support amount). Catalyst C was obtained using support c, in the same manner as in Example <NUM>. The metallic components of catalyst C were <NUM> mass% MoOs (with respect to the total catalyst amount), and <NUM> mass% NiO (with respect to the total catalyst amount). The properties of catalyst C are shown in Table <NUM>.

Catalyst D was obtained in the same manner as in Example <NUM>, except that <NUM> of cobalt carbonate was used instead of nickel carbonate. The metallic components of catalyst D were <NUM> mass% MoOs (with respect to the total catalyst amount), and <NUM> mass% CoO (with respect to the total catalyst amount). The properties of catalyst D are shown in Table <NUM>.

Catalyst E was obtained in the same manner as in Example <NUM>, except that <NUM> of molybdenum oxide, and <NUM> of nickel carbonate were used, and that <NUM> of phosphoric acid was used instead of citric acid. The metallic components of catalyst E were <NUM> mass% MoO<NUM> (with respect to the total catalyst amount), and <NUM> mass% NiO (with respect to the total catalyst amount). The total phosphorus content of the catalyst E, including the phosphorus in the support, was <NUM> mass%. The properties of catalyst E are shown in Table <NUM>.

An alumina support d was obtained in the same manner as in Example <NUM>, except that phosphoric acid was not used. Catalyst F was obtained using support d, in the same manner as in Example <NUM>. The metallic components of catalyst F were <NUM> mass% MoO<NUM> (with respect to the total catalyst amount), and <NUM> mass% NiO (with respect to the total catalyst amount). The properties of catalyst F are shown in Table <NUM>.

An alumina-phosphorus support e was obtained in the same manner as in Example <NUM>, except that <NUM> of phosphoric acid was added. The support e contained <NUM> mass% of phosphorus in terms of P<NUM>O<NUM>, and <NUM> mass% of aluminum in terms of Al<NUM>O<NUM> (the contents are with respect to the total support amount). Catalyst G was obtained using support e, in the same manner as in Example <NUM>. The metallic components of catalyst G were <NUM> mass% MoO<NUM> (with respect to the total catalyst amount), and <NUM> mass% NiO (with respect to the total catalyst amount). The properties of catalyst G are shown in Table <NUM>.

An alumina-phosphorus support f was obtained in the same manner as in Example <NUM>, except that <NUM> of alumina hydrate (A) in terms of an Al<NUM>O<NUM> oxide, and <NUM> of alumina hydrate (B) in terms of an Al<NUM>O<NUM> were mixed. The support f contained <NUM> mass% of phosphorus in terms of P<NUM>O<NUM>, and <NUM> mass% of aluminum in terms of Al<NUM>O<NUM> (the contents are with respect to the total support amount). Catalyst H was obtained using support f, in the same manner as in Example <NUM>. The metallic components of catalyst H were <NUM> mass% MoO<NUM> (with respect to the total catalyst amount), and <NUM> mass% NiO (with respect to the total catalyst amount). The properties of catalyst H are shown in Table <NUM>.

Catalysts A to E of Examples <NUM> to <NUM>, and catalysts F to H of Comparative Examples <NUM> to <NUM> were examined for hydrodemetallation activity and desulfurization activity using a fixed-bed microreactor. The test was conducted under the following conditions. A commercially available demetallation catalyst CDS-DM5 was charged in <NUM>% of the upper stage, whereas a commercially available desulfurization catalyst CDS-R25N or the catalysts A to H were charged in <NUM>% of the lower stage.

Charged catalyst amount: <NUM> (<NUM> of commercially available demetallation catalyst, and catalysts A to H, <NUM> each).

In the activity test, demetallation activity and desulfurization activity (relative activities) were calculated using a reaction rate constant determined from an Arrhenius plot, in which the reaction rate constant from the result of a CDS-DM5/CDS-R25N combined evaluation was assumed to be <NUM>%. The reaction rate constant was determined using the following formula (<NUM>).

The demetallation activity values, and the desulfurization activity values of catalysts A to H are shown in Table <NUM>.

Claim 1:
A hydrotreating catalyst for hydrocarbon oil using an oxide support containing aluminum and phosphorus,
(<NUM>) the oxide support containing <NUM> to <NUM> mass% of phosphorus in terms of P<NUM>O<NUM>,
(<NUM>) the oxide support carrying a metal in Group 6A of the periodic table, and a metal in Group <NUM> of the periodic table,
(<NUM>) the hydrotreating catalyst having a specific surface area of <NUM><NUM>/g or more as measured by the BET method,
(<NUM>) the hydrotreating catalyst having a total pore volume of <NUM> to <NUM>/g as measured by a mercury intrusion method,
(<NUM>) the hydrotreating catalyst having two maximal peaks in a pore diameter range of <NUM> to <NUM> in a log differential pore volume distribution measured by a mercury intrusion method,
(<NUM>) the hydrotreating catalyst having an abrasion strength of <NUM>% or less as measured based on ASTM D4058-<NUM>, and
(<NUM>) the hydrotreating catalyst having a compressive strength of <NUM> N/mm or more as measured using a Kiya hardness meter.