JPH0813328B2 - Catalyst composition for hydrotreatment of hydrocarbon oil and hydrodesulfurization method using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a catalyst composition used for advanced hydrorefining of hydrocarbon oil fractions and hydrocarbon oil residual oil, particularly hydrodesulfurization treatment, More specifically, by adding a specific amount of silica and titania to alumina which is usually used for this type of catalyst carrier, the acidity of the carrier is moderately controlled, and a specific pore distribution is imparted to the catalyst. The present invention relates to a catalyst composition having improved desulfurization activity of hydrogen oil, and a hydrodesulfurization method of hydrocarbon oil using the catalyst composition.

[Prior Art] Conventionally, generally, in a catalytic hydrotreating method for hydrocarbon oils, the refractory oxide carrier is one or two selected from the groups of Group 6B and Group 8 of the Periodic Table. Catalysts supporting more than one metal have been used.

For example, a catalyst for hydrotreatment such as cobalt-molybdenum-based or nickel-molybdenum-based supported on alumina is widely used, and by this, desulfurization, denitrification, hydrodemetallization, deasphaltene, hydrocracking, etc. It is implemented according to various purposes.

The performance required for such a hydrotreating catalyst is high activity and how the performance can be maintained for a long period of time.

For that purpose, first, how much active metal can be carried on a carrier in a highly dispersed state and how many effective active sites can be expressed.

Next, of the target reactants and various catalyst poisoning substances contained in the raw hydrocarbon oil, only the target reactant is efficiently brought close to the active point of the catalyst, and the guard is made to keep the catalyst poisoning substances as close as possible. It is how to retain the function.

As a measure against the former, use a carrier with a high specific surface area.As a measure against the latter, consider the molecular size of the target substance and the molecular size of the catalyst poisoning substance within a range that does not reduce the surface area, and At present, it is proposed and generally practiced to control the pore size.

Further, a catalyst has been proposed in which the acidity is increased by adding silica and titania to alumina to expect decomposition activity rather than desulfurization activity.

[Problems to be Solved by the Invention]

By the way, the conventionally provided catalyst has the following problems.

As for the physical properties of the catalyst, it is good to reduce the average pore size in order to obtain a high surface area in order to enhance the dispersibility of the active metal. However, the small pores are easily blocked by the metal component of the macromolecule which is a catalyst poison.

On the contrary, increasing the average pore diameter is preferable in that the catalyst poisoning substance such as a metal can be accumulated inside the pores. However, the surface area is small and the dispersibility of the active metal is poor.

As described above, what kind of average pore size should be used for activity and life is a very difficult problem.

Also, regarding the addition of silica and titania to alumina, if the acidity is too high, desulfurization activity cannot be expected.

The problem to be solved by the present invention is to develop a hydrotreating catalyst having excellent desulfurization activity.

More specifically, firstly, it is to find an optimum average pore size and pore distribution that are sufficient to enhance the dispersibility of the active metal and do not cause clogging by carbon deposits or hetero compounds that are catalyst poisons. . Secondly, how to provide an acidic point on the catalyst that can maximize the desulfurization activity.

[Means for solving the problem]

The present inventors have conducted extensive studies in order to solve the above-mentioned problems, and as a result, if silica and titania are blended in a fixed ratio in an alumina carrier, the alumina carrier has an acid property that is more favorable for desulfurization than decomposition. In addition, it has been found that the catalyst has a specific average pore diameter and a specific pore distribution, and such a catalyst further enhances the desulfurization activity of hydrocarbons, thus completing the present invention.

That is, the present invention provides (1) a catalyst carrier comprising alumina, silica, and titania, which contains, as a catalytically active component, at least one metal selected from Group 6B of the periodic table in an amount of 7 to 25 in terms of oxide based on the catalyst.
%, And at least 1 selected from Group 8 of the periodic table
3 to 6% by weight of a metal of the catalyst is calculated in terms of oxide, and silica and titania in the catalyst carrier are 1 to 10% by weight on the carrier basis, and the pore characteristics of the catalyst are , (1) The average pore diameter measured by the mercury porosimeter press-fitting method is 50 to 100Å, (2) The volume occupied by pores with an average pore diameter of 50 to 100Å is at least 50% of the total pore volume, and (3) ratio. A surface area of at least 150 m ² / g, (4) a total pore volume of 0.4 to 1.5 ml / g, a catalyst composition for hydrotreating a hydrocarbon oil, and (2) the above catalyst A method for hydrodesulfurizing a hydrocarbon oil characterized by using a composition.

The "total pore volume" in the present invention is not possible to measure the volume of all existing pores, so the mercury absorption amount at 4225 Kg / cm ² · G (60000 psig) measured by a mercury porosimeter is the total fine pore volume. What is regarded as the pore volume.

The value of the "average pore diameter" in the present invention, the relationship between the absorption of mercury under pressure with a catalyst mercury porosimeter obtained for 0~4225Kg / cm ² · G, the amount absorbed in the 4225Kg / cm ² · G The average pore diameter is obtained from the pressure when the absorption amount of 1/2 is shown. In the present invention, the contact angle of mercury was 130 ° and the surface tension was 470 dyne / cm. The relationship between the mercury porosimeter and the pressure and the corresponding pore size is already known.

The average pore diameter of the catalyst of the present invention is about 50 to 100Å, preferably about 60 to 95Å. If the average pore diameter is too small,
A carbonaceous substance or a hetero molecule, which is a catalyst poison, is deposited on the surface, and it becomes difficult for the hydrocarbon oil, which is a reactant, to diffuse into the inside of the pores, and desulfurization is reduced. On the other hand, if the average pore diameter is too large, the specific surface area decreases and the hydrodesulfurization activity decreases.

The volume of pores having an average pore diameter of 50 to 100Å of the catalyst of the present invention is at least about 50%, preferably 70% or more of the total pore volume of the catalyst. As described above, even if it has a specific average pore diameter, if the volume occupied by the pores having an average pore diameter of 50 to 100 Å is too small, the desulfurization activity will decrease.

Surface area i.e. the specific surface area per unit weight of the catalyst of the present invention, at least about 150 meters ² / g, preferably about 200 to 300 m ² /
g or more. If the specific surface area is too small, the number of active sites is reduced and excellent desulfurization activity is not exhibited.

The total pore volume of the catalyst of the present invention is about 0.4 to 1.5 ml / g, preferably about 0.45 to 0.8 ml / g. When the proportion of the total pore volume is small, the resistance to poisonous substances is small and it cannot be practically used.

The catalyst of the present invention is a hydrotreating catalyst in which effective metal components of Groups 6B and 8 of the Periodic Table are supported on a carrier substantially composed of alumina, silica and titania.

As the alumina which is a part of the carrier, γ-alumina,
Any one of χ-alumina and η-alumina or a mixture thereof is suitable.

In the carrier of the catalyst of the present invention, silica and titania are each about 1 to 10% by weight, preferably about 3 to 8% by weight, based on the carrier. If the amount is too small, a suitable acid strength required as a catalyst cannot be obtained, which is not suitable for deep desulfurization. If too much, the essential desulfurization activity is reduced.

The catalyst of the present invention can be prepared by a usual preparation method.

As a method for preparing the alumina-silica-titania carrier,
Alumina, silica and titania gels are prepared in advance, a method of mixing these, silica gel, a method of precipitating alumina gel on silica gel and titania gel after immersing the titania gel in a solution of an aluminum compound, a water-soluble aluminum compound, A method of adding a basic substance to a homogeneous mixed solution of a water-soluble silicon compound and a water-soluble titanium compound and coprecipitating the three can be adopted.

A particularly preferable preparation method is a method in which each gel of alumina, silica and titania is prepared in advance and then these are mixed.

As a method for preparing the alumina gel, a known method can be used.

For example, an aluminum salt such as aluminum sulfate or aluminum nitrate is neutralized with a base such as ammonium, or an aluminate such as sodium aluminate is neutralized with an acidic aluminum salt or acid, and the formed gel is washed. Obtainable. It can also be obtained by hydrolyzing an aluminum alkoxide.

As a method for preparing silica gel, a known method can be used.

For example, water glass is dissolved in ion-exchanged water, sulfuric acid is appropriately added to the solution, and the suspension is heated to about 50 to 90 ° C while adjusting the pH to about 6.0 to 11.0, and at least 1 to 1
Hold for 3 hours. After that, the precipitate was filtered with a filter,
It can be obtained by washing with ammonium carbonate and water to remove impurity ions. It can also be obtained by hydrolyzing an alkoxysilane. As a method for preparing the titania gel, a known method can be used.

For example, titanium sulfate, chloride, and nitrate are diluted with ion-exchanged water, aqueous ammonia, nitrate, etc. are appropriately added to the aqueous solution, and the suspension is adjusted to about 50-
Heat to 90 ° C. and hold for at least 1-3 hours. Then, the precipitate can be filtered off, washed with ammonium carbonate and water to remove impurity ions, and obtained. It can also be obtained by hydrolyzing a titanium alkoxide.

Next, these three gels are physically mixed and dried using a spray dryer or the like. The gel thus obtained, in order to obtain specific pores or pore distribution, under desired conditions, after molding by an extrusion molding machine, dried,
The carrier is obtained by calcining at about 400 to 700 ° C. for about 1 to 5 hours.

The carrier is usually formed into shaped particles by methods well known in the art. A preferred method is to provide a precursor of the desired carrier, for example, an inorganic refractory oxide gel, such as a spray dried or peptized alumina-silica-titania gel, through a die having openings of the desired size and shape. This is a method of extruding and then cutting the extruded pieces to a desired length.

In preparing the catalyst of the present invention, it is preferable that the carrier particles initially have a pore volume distribution similar to that of the final catalyst, but this is not always necessary. Here, it should be noted that when the carrier particles carry active metals such as nickel and molybdenum, the contact angle of mercury changes, and therefore, generally, the pore diameter is about 10 to 20 Å more than the carrier particles. It tends to shift to a larger value. Therefore, even if the average pore diameter of the carrier particles is slightly smaller than the desired value, the final catalyst composition required here can be obtained by the subsequent impregnation, calcination and catalyst preparation steps.

In order to express the above-mentioned characteristics which are the characteristics of the catalyst of the present invention, an acid and a basic nitrogen compound are added to alumina gel or titanigel at the time of carrier preparation, or polyvinyl alcohol, polyethylene glycol, crystalline cellulose, etc. It is desirable to add an organic molding aid or an alcohol such as methyl alcohol, ethyl alcohol or n-butyl alcohol.

The method for supporting the Group 6B metal and Group 8 metal components on the carrier can also be carried out by a usual method.

For example, the carrier is immersed in a solution containing these hydrogenation-active metal components, or the carrier and this solution are mixed,
This solution is dropped onto the carrier, or a hydrogenation-active metal component is deposited on the carrier by adding a precipitant for the hydrogenation-active metal component while the carrier is immersed in the solution. A method of supporting the hydrogenation active metal component on the carrier by bringing it into contact with the solution containing it can be adopted.

Further, as for the carrying order of the 6B group and the 8th group of the periodic table, either one may come first, or both may be carried simultaneously.

Examples of molybdenum compounds that can be used as a solution of Group 6B metal of the periodic table include ammonium paramolybdate, molybdic acid, ammonium molybdate, ammonium phosphomolybdate, phosphomolybdic acid, and the like.
Further, as a nickel compound which can be used as a solution of Group 8 metal of the periodic table, for example, nickel nitrate, sulfate,
There are fluorides, chlorides, bromides, acetates, carbonates, phosphates, etc. In addition to these, metal compounds of Group 6B and Group 8 of the periodic table known to those skilled in the art as usable in this type of field can be used.

After the treatment as described above, it is preferable to carry out drying and baking by a usual method.

Drying is usually at room temperature to about 150 ° C, especially about 100 to 120
It is preferable to hold at about 5 hours or more, particularly about 12 to 24 hours, and the firing is usually from room temperature to about 350 to 600 ° C, especially about 400 to 550 ° C, about 3 hours or more, especially about 12 to 12 hours. It is preferable to hold it for 24 hours.

The catalyst of the present invention is usually about 7 to 25% by weight, preferably about 10 to 20% by weight, of 6B, calculated as oxide, based on the catalyst.
Group metal and about 3 to 6% by weight, preferably about 3 to 5% by weight
And a Group 8 metal of It is considered that most of these hydrogenation-active metal components become oxides and some become elemental elements in the above-mentioned catalyst after calcination.

When the catalyst of the present invention is used in the form of sulfide, it is pre-sulfided.

As the sulfurization method, a method of passing a hydrocarbon oil or a gas phase sulfide containing about 1.0% by weight or more of sulfur on a catalyst under high temperature and high pressure is adopted.

 The physical properties of the catalyst of the present invention detailed above are shown in Table 1.

Hydrocarbon oils applicable to the process of the present invention using the catalyst of the present invention include atmospheric distillate distillates and residues of crude oil, vacuum distillate distillates and residues, visbreaking oils, tar sands oils, and shale. Examples include oil.

In particular, the catalyst of the present invention is a medium distillate oil such as a kerosene fraction and a light oil fraction, a heavy distillate oil under reduced pressure distillation, a residual oil containing asphalt, or a hydrotreatment of these mixed oils. It is suitable for

Further, the hydrotreating condition in the method of the present invention is that the temperature is about
200-450 ℃, Pressure about 10-200Kg / cm ² , LHSV (Liquid space velocity)
It is preferably about 0.1 to 5.0 Hr ^-1 .

[Action]

In the catalyst of the present invention, since silica and titania are contained in the alumina carrier, silica atoms or titanium atoms and oxygen atoms chemically bond with aluminum atoms on alumina to form new acidic points and hydrogenate. Improves desulfurization activity of active metals.

At this time, since silica and titania are contained in a specific ratio, the above-mentioned acidic point is more convenient for desulfurization than decomposition of hydrocarbon oil.

Further, in the catalyst of the present invention, by strictly controlling the average pore diameter and the pore distribution of the catalyst, the diffusion of the target reactant into the catalyst is promoted, and resistance to the catalyst poisoning substance is imparted, and Improves desulfurization activity.

In the method of the present invention, by using such a catalyst of the present invention in the hydrotreatment of a hydrocarbon oil, the target substance in the hydrocarbon oil can be easily transferred to the inside of the catalyst supporting the hydrogenation active metal having high desulfurization activity. And desulfurization with high efficiency, and at the same time, the deterioration of the catalytic activity of the present invention due to the catalyst poisoning substance in the hydrocarbon oil is suppressed as much as possible.

Incidentally, the "hydrotreatment" in the present invention refers to a treatment by contacting a hydrocarbon oil with hydrogen, and comprises hydrorefining with relatively low severity of reaction conditions, and some cracking reaction with relatively high severity. It involves hydrorefining, hydroisomerization, hydrodealkylation, and other reactions of hydrocarbon oils in the presence of hydrogen.

For example, it includes hydrodesulfurization, hydrodenitrogenation, hydrocracking of distillate and residual oil of atmospheric distillation or vacuum distillation, and hydrorefining of kerosene fraction, gas oil fraction, wax, lubricating oil fraction. Etc. are included.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.

Example 1 Aluminum-sec-butoxide 200 g, titanium tetraisopropoxide 8.64 g and tetraethoxysilane 16.42 g
Is dissolved in isopropanol 4 and stirred at 80 ° C. for 1 hour.

When 1 kg of ion-exchanged water was gradually added dropwise to this solution, a white precipitate was formed, and finally a milky white slurry was formed. Further, the slurry is kept stirring at 80 ° C. for 3 hours.

After filtering the obtained slurry with a filter, it is heated and concentrated to give a plastic gel, and the gel is extruded while adjusting the pressure to obtain the desired pore distribution, dried and fired to form a catalyst carrier. did.

20 g of this carrier was weighed, and 4.7 g of ammonium molybdate dissolved in 14.5 ml of ion-exchanged water was added to this, and 1
It was soaked for an hour, air-dried, and baked at 500 ° C. for 12 hours.

Then, 4.5 ml of ion-exchanged water containing 5 g of cobalt nitrate was impregnated, air-dried, and calcined at 500 ° C. for 12 hours to obtain a catalyst.

The obtained catalyst contained 4.9% by weight of cobalt oxide and 14.9% by weight of molybdenum oxide. Further, titania and silica were contained in an amount of 5% by weight, respectively, based on the weight of the carrier.

The specific surface area of this catalyst is 321 m ² / g, the pore volume is 0.65 ml / g,
The average pore diameter determined by the mercury porosimeter press-fitting method was 80Å.

Further, the volume occupied by 50 to 100 Å pores was 80% of the total pore volume (catalyst A).

Example 2 233 g of aluminum nitrate was dissolved in 600 ml of ion-exchanged water, and this aqueous solution was added to a mixed liquid of 280 g of 28% ammonia water and 600 ml of ion-exchanged water while stirring. At this time, the pH of the aqueous solution was kept at 9 or higher, and the suspension thus formed was filtered after standing for 4 hours. The separated precipitate was kept and matured in 800 ml of 1N ammonium carbonate aqueous solution at 50 ° C. for 12 hours, cooled, and filtered again. Then, it was further washed with 0.2% ammonia water 1.2 and filtered to obtain a precipitate.

Separately, water glass (containing 3.8% by weight of silica) 8
6 g was dissolved in 800 ml of ion-exchanged water, and a 5N sulfuric acid aqueous solution was gradually added dropwise to this aqueous solution with stirring until the pH reached 7.5. After stirring for 2 hours as it was, the resulting suspension was filtered. The separated precipitate was washed 5 times with ion-exchanged water 5 to obtain a precipitate.

Furthermore, 110 g of 30% titanium nitrate solution is added to 600 ml of deionized water.
The mixture was diluted with and a 10% aqueous ammonia solution was added dropwise to the solution with stirring until the pH reached 6. After stirring for 1 hour as it was, the resulting suspension was filtered. The separated precipitate was washed 3 times with ion-exchanged water 3 to obtain a precipitate.

The above precipitates (1) to (5) were mixed and thoroughly kneaded with a kneader. After that, adjust the water content, extrude while adjusting the pressure to obtain the desired pore distribution, air dry, then 500 ° C.
After firing for 5 hours, a carrier was obtained.

20 g of the above carrier is weighed, and 4.7 g of ammonium molybdate dissolved in 12.5 ml of ion-exchanged water is added to this, and 1
It was soaked for an hour, air-dried, and baked at 450 ° C. for 12 hours.

Next, 4.5 ml of ion-exchanged water containing 5 g of cobalt nitrate was impregnated, air-dried, and calcined at 450 ° C. for 12 hours to obtain a catalyst.

The obtained catalyst contained 4.9% by weight of cobalt oxide and 14.9% by weight of molybdenum oxide. Further, titania and silica were contained in an amount of 10% by weight and 5% by weight, respectively, based on the weight of the carrier.

The specific surface area of this catalyst is 250 m ² / g, the pore volume is 0.48 ml / g,
The average pore diameter determined by the mercury porosimeter press-fitting method was 73Å.

The volume occupied by 50 to 100 Å pores was 87% of the total pore volume. (Catalyst B).

Example 3 The precipitate of Example 2 was prepared in exactly the same manner as in Example 2.

Separately, water glass (containing 3.8% by weight of silica) 1
67 g was dissolved in 1000 ml of ion-exchanged water, and a 5N sulfuric acid aqueous solution was gradually added dropwise to the solution while stirring the solution until the pH reached 7.5. After stirring for 2 hours as it was, the resulting suspension was filtered. The separated precipitate was washed 5 times with ion-exchanged water 7 to obtain a precipitate.

Furthermore, 21.1 g of 30% titanium sulfate solution was added to 200 ml of ion-exchanged water.
The mixture was diluted with and a 10% aqueous ammonia solution was added dropwise to the solution with stirring until the pH reached 6. After stirring for 1 hour as it was, the resulting suspension was filtered. The separated precipitate was washed 5 times with ion-exchanged water 1 to obtain a precipitate.

The above precipitates (1) to (5) were mixed and thoroughly kneaded with a kneader. After that, adjust the water content, extrude while adjusting the pressure to obtain the desired pore distribution, air dry, then 500 ° C.
After firing for 5 hours, a carrier was obtained.

20 g of the above carrier is weighed, and 4.7 g of ammonium molybdate dissolved in 12.5 ml of ion-exchanged water is added to this, and 1
It was soaked for an hour, air-dried, and baked at 450 ° C. for 12 hours.

Next, 4.5 ml of ion-exchanged water containing 5 g of nickel nitrate was impregnated, air-dried, and calcined at 450 ° C. for 12 hours to obtain a catalyst.

The obtained catalyst contained 4.7% by weight of nickel oxide and 14.8% by weight of molybdenum oxide. Further, titania and silica were contained in an amount of 2% by weight and 10% by weight, respectively, based on the weight of the carrier.

The specific surface area of this catalyst is 301 m ² / g, the pore volume is 0.52 ml / g,
The average pore diameter determined by the mercury porosimeter press-fitting method was 65Å.

The volume occupied by 50-100 Å pores is 8% of the total pore volume.
5% (catalyst C).

Comparative Example 1 The precipitate of Example 2 was prepared in exactly the same manner as in Example 2.

This was thoroughly kneaded with a kneader. Then, the water content was adjusted, extrusion molding was performed while adjusting the pressure to obtain a desired pore distribution, air-dried, and then baked at 500 ° C. for 5 hours to obtain a carrier.

20 g of the above carrier is weighed, and 4.7 g of ammonium molybdate dissolved in 12.5 ml of ion-exchanged water is added to this, and 1
It was soaked for an hour, air-dried, and baked at 450 ° C. for 12 hours.

Next, 4.5 ml of ion-exchanged water containing 5 g of cobalt nitrate was impregnated, air-dried, and calcined at 450 ° C. for 12 hours to obtain a catalyst.

The obtained catalyst contained 4.9% by weight of cobalt oxide and 14.9% by weight of molybdenum oxide. In addition, no carrier other than alumina was detected in the carrier.

The specific surface area of this catalyst is 260 m ² / g, the pore volume is 0.59 ml / g,
The average pore diameter determined by the mercury porosimeter press-fitting method was 88Å.

Further, the volume occupied by 50 to 100 Å pores was 80% of the total pore volume (catalyst D).

Comparative Example 2 The precipitate of Example 2 was prepared in exactly the same manner as in Example 2.

Separately, water glass (containing 3.8% by weight of silica) 1
64 g was dissolved in 1000 ml of ion-exchanged water, and a 5N sulfuric acid aqueous solution was gradually added dropwise to the solution while stirring until the pH was 7.5. After stirring for 2 hours as it was, the resulting suspension was filtered. The separated precipitate was washed 5 times with ion-exchanged water 5 to obtain a precipitate.

The above-mentioned precipitates were mixed and thoroughly kneaded with a kneader. After that, adjust the water content, extrude while adjusting the pressure to obtain the desired pore distribution, air dry, then 500 ° C.
After firing for 5 hours, a carrier was obtained.

20 g of the above carrier was weighed, and 4.7 g of ammonium molybdate dissolved in 14.0 ml of ion-exchanged water was added to this, and 1
It was soaked for an hour, air-dried, and baked at 450 ° C. for 12 hours.

Next, 4.5 ml of ion-exchanged water containing 5 g of nickel nitrate was impregnated, air-dried, and calcined at 450 ° C. for 12 hours to obtain a catalyst.

The obtained catalyst contained 4.8% by weight of nickel oxide and 15.0% by weight of molybdenum oxide. Further, silica was contained in an amount of 10% by weight based on the weight of the carrier.

The specific surface area of this catalyst is 320 m ² / g, the pore volume is 0.50 ml / g,
The average pore diameter determined by the mercury porosimeter press-fitting method was 61Å.

The volume occupied by 50 to 100 Å pores was 80% of the total pore volume (catalyst E).

Comparative Example 3 The precipitate of Example 2 was prepared in exactly the same manner as in Example 2.

Further, 49 g of a 30% titanium sulfate solution was diluted with 300 ml of ion-exchanged water, and a 10% aqueous ammonia solution was added dropwise to the solution with stirring until the pH reached 6. After stirring for 1 hour as it was, the resulting suspension was filtered. The separated precipitate was washed 5 times with ion-exchanged water 2 to obtain a precipitate.

The above-mentioned precipitates were mixed and thoroughly kneaded with a kneader. After that, adjust the water content, extrude while adjusting the pressure to obtain the desired pore distribution, air dry, then 500 ° C.
After firing for 5 hours, a carrier was obtained.

20 g of the above carrier is weighed, and 4.7 g of ammonium molybdate dissolved in 13.0 ml of ion-exchanged water is added to this, and 1
It was soaked for an hour, air-dried, and baked at 450 ° C. for 12 hours.

Next, 4.5 ml of ion-exchanged water containing 5 g of cobalt nitrate was impregnated, air-dried, and calcined at 450 ° C. for 12 hours to obtain a catalyst.

The obtained catalyst contained 5.0% by weight of cobalt oxide and 14.9% by weight of molybdenum oxide. Further, titania was contained in an amount of 5% by weight based on the weight of the carrier.

The specific surface area of this catalyst is 282 m ² / g, the pore volume is 0.51 ml / g,
The average pore diameter determined by the mercury porosimeter press-fitting method was 69Å.

Further, the volume occupied by 50 to 100 Å pores was 80% of the total pore volume (catalyst F).

Comparative Example 4 The precipitate of Example 2 was prepared in exactly the same manner as in Example 2.

Separately, water glass (containing 3.8% by weight of silica) 4
91 g was dissolved in ion-exchanged water 2, and a 5N sulfuric acid aqueous solution was gradually added dropwise to this solution with stirring until the pH reached 7.5. After stirring for 2 hours as it was, the resulting suspension was filtered. The separated precipitate was washed 5 times with ion-exchanged water 10 to obtain a precipitate.

Furthermore, 310 g of 30% titanium sulfate solution is added to ion-exchanged water 1.5.
The mixture was diluted with and a 10% aqueous ammonia solution was added dropwise to the solution with stirring until the pH reached 6. After stirring for 1 hour as it was, the resulting suspension was filtered. The separated precipitate was washed 5 times with ion-exchanged water 8 to obtain a precipitate.

The above precipitates (1) to (5) were mixed and thoroughly kneaded with a kneader. After that, adjust the water content, extrude while adjusting the pressure to obtain the desired pore distribution, air dry, then 500 ° C.
After firing for 5 hours, a carrier was obtained.

20 g of the above carrier was weighed, and 4.7 g of ammonium molybdate dissolved in 12.0 ml of ion-exchanged water was added to this, and 1
It was soaked for an hour, air-dried, and baked at 450 ° C. for 12 hours.

Next, 4.5 ml of ion-exchanged water containing 5 g of cobalt nitrate was impregnated, air-dried, and calcined at 450 ° C. for 12 hours to obtain a catalyst.

The obtained catalyst contained 4.9% by weight of cobalt oxide and 15.1% by weight of molybdenum oxide. In addition, titania and silica are 20% by weight and 20% by weight, respectively, based on the weight of the carrier.
Each was included.

The specific surface area of this catalyst is 163 m ² / g, the pore volume is 0.39 ml / g,
The average pore diameter determined by the mercury porosimeter press-fitting method was 88Å.

The volume occupied by 50 to 100 Å pores was 62% of the total pore volume (catalyst G).

Comparative Example 5 The precipitate of Example 2 was prepared in exactly the same manner as in Example 2.

Each of the precipitates was first spray-dried, calcined, water was added again to adjust the humidity, and the kneader was sufficiently kneaded. afterwards,
It was extruded while adjusting the pressure to obtain a desired pore distribution, air-dried, and then calcined at 500 ° C. for 5 hours to obtain a carrier.

20 g of the above carrier is weighed, and 4.7 g of ammonium molybdate dissolved in 12.5 ml of ion-exchanged water is added to this, and 1
It was soaked for an hour, air-dried, and baked at 450 ° C. for 12 hours.

Next, 4.5 ml of ion-exchanged water containing 5 g of cobalt nitrate was impregnated, air-dried, and calcined at 450 ° C. for 12 hours to obtain a catalyst.

The obtained catalyst contained 4.7% by weight of cobalt oxide and 14.8% by weight of molybdenum oxide. Further, titania and silica were contained in an amount of 10% by weight and 5% by weight, respectively, based on the weight of the carrier.

The specific surface area of this catalyst is 185 m ² / g, the pore volume is 0.53 ml / g,
The average pore diameter determined by the mercury porosimeter press-fitting method is 120Å
Met.

The volume occupied by 50 to 100 Å pores was 35% of the total pore volume (catalyst H).

Table 2 shows the physical properties of the catalysts A to H prepared in the above Examples 1 to 3 and Comparative Examples 1 to 5.

Further, the catalysts A to H obtained in the above Examples 1 to 3 and Comparative Examples 1 to 3 were evaluated by a hydrodesulfurization relative activity evaluation test under the following conditions.

Relative activity evaluation test for hydrodesulfurization: Fixed bed type reaction tube with inner diameter of 10 mmφ was used for hydrodesulfurization relative activity against Arabian light gas oil (LGO), vacuum gas oil (VGO) or Arabian heavy atmospheric residual oil (AH-AR) ,
Day 10 (condition 1), day 20 (condition 2), day 25 (condition 3)
(The sulfur content of the product is low at the beginning of the reaction, but since it increased and stabilized with the number of days, it was set as the 10th, 20th, and 25th days.)
The initial relative desulfurization activity obtained from the residual sulfur content (% by weight) of the reaction product of was determined.

The properties and reaction conditions of the feedstock are shown in Table 3, and the results are shown in Table 4.
Table (light diesel oil), Table 5 (vacuum diesel oil) and Table 6 (normal pressure residual oil) are shown.

As is clear from Table 4, catalysts A of Examples 1 to 3
All of Examples 4 to 6 using C show excellent results in light-gas light oil efflux activity as compared with Comparative Examples 6 to 10 using catalysts D to H of Comparative Examples 1 to 5. I understand.

As is clear from Table 5, catalysts A of Examples 1 to 3
Examples 7 to 9 using C all showed excellent results in desulfurization activity of vacuum gas oil as compared with Comparative Examples 11 to 14 using catalysts DG of Comparative Examples 1 to 4. I understand.

As is clear from Table 6, Examples 10 and 11 using the catalysts A and B of Examples 1 and 2 are the same as Comparative Examples 15 and 16 using the catalysts D and H of Comparative Examples 1 and 5, respectively. By comparison, it can be seen that the results show that the desulfurization activity of the atmospheric residue is excellent.

〔The invention's effect〕

The catalyst of the present invention is newly formed at an acidic point convenient for desulfurization of hydrocarbon oil, and further has good diffusion of the target reactant into the catalyst, and has excellent resistance to a catalyst poisoning substance, The desulfurization activity of hydrocarbon oil is greatly improved.

In the method of the present invention, by using the above-mentioned catalyst of the present invention, as shown in Tables 4 to 6, as compared with the conventional hydrorefining method for hydrocarbon oils, any one of petroleum distillates and residual oils can be obtained. It is possible to perform desulfurization with high efficiency even for feedstock oil,
In particular, it shows a remarkable effect on petroleum distillate raw materials.

Claims (2)

[Claims] 1. A catalyst carrier composed of alumina, silica and titania, and 7 to 25% by weight in terms of oxide, based on the catalyst, of at least one metal selected from Group 6B of the periodic table as a catalytically active component, and Based on the catalyst, at least one metal selected from Group 8 of the periodic table is 3 to 3 in terms of oxide.
6 wt% of the carrier, silica and titania in the catalyst carrier are 1 to 10 wt% respectively on the carrier basis, and the pore characteristics of the catalyst are (1) the average fineness measured by the mercury porosimeter press-fitting method. Pore diameter is 50-100Å, (2) Volume occupied by pores with average pore diameter of 50-100Å is at least 50% of total pore volume, (3) Specific surface area is at least 150 m ² / g, (4) Fine pore A catalyst composition for hydrotreating a hydrocarbon oil, which has a pore volume of 0.4 to 1.5 ml / g. 2. A method for hydrodesulfurizing a hydrocarbon oil, which comprises using the catalyst composition according to claim 1.