JPH03275143A - Catalyst composition for hydrogen-processing hydrocarbon oil and hydrodesulfurization metho using the same - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a catalyst composition used for hydrocarbon oil residue and advanced hydrorefining of hydrocarbon oil residue, particularly hydrodesulfurization treatment. By adding specific amounts of silica and titania to alumina, which is normally used for this type of catalyst carrier, the acidity of the carrier can be appropriately controlled, and a specific pore distribution can be imparted to the catalyst. The present invention relates to a catalyst composition with improved oil desulfurization activity and a hydrodesulfurization method for hydrocarbon oil using this catalyst composition.

[Conventional technology]

Conventionally, in general, in the catalytic hydrotreating method of hydrocarbon oil, one or more metals selected from Group 6B of the Periodic Table and Group 8 of the Periodic Table are added to a refractory oxide carrier. Supported catalysts are used.

For example, hydrotreating catalysts such as cobalt-molybdenum or nickel-molybdenum supported on aluminum are widely used, and are used for desulfurization, denitrification, hydrodemetallization, asphaltenization, and hydrocracking. etc. are being implemented for various purposes.

The performance required of such a catalyst for hydrotreating is high activity and the ability to maintain this performance for a long period of time.

To this end, the first step is to support the active metal in a large amount and in a highly dispersed state on the carrier, and to express a large amount of effective active sites.

Next, among the target reactant and various catalyst poisoning substances contained in the feedstock hydrocarbon oil, only the target reactant is efficiently brought close to the active site of the catalyst, and the catalyst poisoning substance is not exposed to the front as much as possible. The key is how to maintain the guard function.

A measure for the former is to use a carrier with a high specific surface area, and a measure for the latter is to improve the fineness of the catalyst while taking into account 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. Controlling the pore size has been proposed and is currently commonly practiced.

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

[Problem to be solved by the invention]

However, the conventionally provided catalysts have the following problems.

Regarding the physical properties of the catalyst, reducing the average pore diameter in order to obtain a high surface area is good in terms of increasing the dispersibility of the active metal. However, the small pores are easily blocked by the metal components of macromolecules that act as catalyst poisons.

On the other hand, it is preferable to increase the average pore diameter because it allows catalyst poisoning substances such as metals to accumulate inside the pores. However, the surface area is small and the dispersibility of the active metal is poor.

As described above, it is an extremely difficult problem to decide what average pore diameter should be used in terms of activity and life.

Furthermore, when silica and titania are added to alumina, desulfurization activity cannot be expected if the acidity is too high.

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

More specifically, the first step is to find the optimal average pore diameter and pore distribution that are sufficient to enhance the dispersibility of the active metal and that do not cause blockage due to catalyst poisons such as carbon precipitates and hetero compounds. . The second problem is how to provide acidic points on the catalyst that can maximize desulfurization activity.

[Means to solve the problem]

In order to solve the above problems, the present inventors have conducted extensive research and found that if silica and titania are blended into an alumina carrier in a certain proportion, the carrier will have acidic properties that are more favorable for desulfurization than for decomposition. The present inventors have discovered that the catalyst has a specific average pore diameter and pore distribution, and that such a catalyst further increases hydrocarbon desulfurization activity, leading to the completion of the present invention.

That is, the present invention provides: (1) At least one metal selected from Group 6B of the Periodic Table is added to a catalyst carrier consisting of alumina, silica, and titania as a catalytically active component in an amount of 7 to 7 to 70% in terms of oxide on a catalyst basis.
25% by weight, and 3 to 6% by weight of at least one metal selected from Group 8 of the Periodic Table in terms of oxide based on the catalyst, and the silica and titania in the catalyst carrier are each supported on the basis of the carrier. 1 to 10% by weight, and the pore characteristics of the catalyst are as follows: (1) The average pore diameter measured by mercury porosimeter intrusion method is 50 to 100.

(2) The volume occupied by pores with an average pore diameter of 50 to 100 is at least 50% of the total pore volume.

(3) Specific surface area of at least 150 m”7g.

(4) Total pore volume is 0.4 to 1.5 mff1/g.

A catalyst composition for hydrotreating hydrocarbon oil, characterized in that: and (2) a method for hydrogenating WA sulfur hydrocarbon oil, characterized in that the above-mentioned catalyst composition is used. do.

In the present invention, the "total pore volume" means 4225 Kg/cm2-G (600
The amount of mercury absorbed at 00 ps ig) is considered to be the total pore volume.

In addition, the value of the "average pore diameter" in the present invention is determined by determining the relationship between the pressure of a mercury porosimeter and the amount of mercury absorbed by the catalyst from 0 to 4225 Kg/Cm2・G.
The average pore diameter was determined from the pressure at which the absorption amount was 1/2 of the absorption amount in Kg/crn”G.In the present invention, the contact angle of mercury is 130°, and the surface tension is It was determined as 470 dyne/cm.The relationship between mercury porosimeter, pressure, and the corresponding pore diameter is already known.

The average pore diameter of the catalyst of the present invention is about 50 to 100 pores, preferably about 60 to 95 pores. If the average pore diameter is too small, carbonaceous substances and petromolecules, which are catalyst poisons, are deposited on the surface, making it difficult for hydrocarbon oil, which is a reactant, to diffuse into the pores, and desulfurization is reduced. Conversely, if the average pore diameter is too large, the specific surface area will decrease and the hydrodesulfurization activity will decrease.

The volume occupied by pores having an average pore diameter of 50 to 100 in the catalyst of the present invention is at least about 50%, preferably 70% or more, of the total pore volume of the catalyst. As mentioned above, even if the average pore diameter is 50 to 10
If the volume occupied by the pores is too small, the desulfurization activity will decrease.

The surface area per unit weight or specific surface area of the catalyst of the present invention is at least about 150 m2/g, preferably about 200 m2/g.
~300 m''/g or more. If the specific surface area is too small, the number of active sites will decrease and excellent desulfurization activity will not be exhibited.

The total pore volume of the catalyst of the present invention is approximately 0.4 to 1.5 ml.
/g, preferably about 0.45-0.8 mI! , 7g. If the proportion of the total pore volume is small, the resistance to poisonous substances will be low and it will not be practical.

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 consisting essentially of alumina, silica, and titania.

The alumina that is part of the carrier includes γ-alumina, χ
-Alumina, η-alumina, or a mixture thereof is preferred.

In the carrier of the catalyst of the present invention, silica and titania are each present in an amount of about 1 to 10% by weight, preferably about 3 to 8% by weight, based on the carrier. If it is too small, the appropriate acid strength required as a catalyst cannot be obtained, making it unsuitable for deep desulfurization. If it is too large, the essential desulfurization activity will decrease.

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

The method for preparing the alumina silica titania support is to prepare alumina, silica and titania gels in advance and mix them together, or to immerse the silica gel and titania gel in a solution of an aluminum compound, and then add the alumina gel. method for depositing on silica gel and titania gel;
A method may be adopted in which a basic substance is added to a uniform mixed solution of a water-soluble aluminum compound, a water-soluble silicon compound, and a water-soluble titanium compound, and the three are co-precipitated.

A particularly preferred preparation method is a method in which gels of aluminum, silica, and titania are prepared in advance and then mixed.

A known method can be used to prepare the alumina gel.

For example, aluminum salts such as aluminum sulfate and aluminum nitrate are neutralized with a base such as ammonium, or aluminates such as sodium aluminate are neutralized with acidic aluminum salts or acids, and the resulting gel is washed. Obtainable.

It can also be obtained by hydrolyzing aluminum alkoxide.

A known method can also be used for preparing silica gel.

0 For example, water glass is dissolved in ion-exchanged water, sulfuric acid is added to the solution as appropriate, and the suspension is heated to about 50 to 90°C while adjusting the pH to about 6.0 to 11.0. and hold for at least 1-3 hours.

Thereafter, the precipitate is separated using a filter and washed with ammonium carbonate and water to remove impurity ions. It can also be obtained by hydrolyzing alkoxysilane.

A known method can also be used to prepare titania gel.

For example, titanium sulfates, chlorides, and nitrates are diluted with ion-exchanged water, and aqueous ammonia, nitrates, etc. are added as appropriate to the aqueous solution, and while adjusting the pH, this suspension is mixed to about 50%
Heat to ~90°C and hold for at least 1-3 hours.

Thereafter, the precipitate is separated using a filter and washed with ammonium carbonate and water to remove impurity ions. It can also be obtained by hydrolyzing titanium alkoxide.

Next, these three types of gels are physically mixed and dried using a spray dryer or the like. In order to obtain specific pores or pore distribution, the gel thus obtained is molded using an extrusion molding machine under desired conditions, and then dried at approximately 400 to 700°C for approximately 1 to 5 A carrier is obtained by firing for a period of time.

The carrier is usually formed into shaped particles by methods well known in the art. A preferred method involves applying a precursor of the desired carrier, e.g., an inorganic refractory oxide gel such as spray-dried or decoagulated Aldansuichi silica titania gel, to a die having openings of the desired size and shape. In this method, the extruded material is extruded into a desired length.

In preparing the catalyst of the present invention, it is advantageous, but not necessary, for the initial support particles to have a pore volume distribution similar to that of the final catalyst. What should be noted here is that
When active metals such as nickel and molybdenum are supported on carrier particles, the contact angle of mercury changes; therefore, in boat fishing, the pore diameter shifts to a value approximately 10 to 20 times larger than that of the carrier particles. It is a trend. Therefore, even if the average pore diameter of the carrier particles is slightly smaller than the desired value, the required final catalyst composition can be obtained through the subsequent impregnation, calcination and catalyst preparation steps.

In order to exhibit the above-mentioned physical properties that are characteristic of the catalyst of the present invention, it is necessary to add an acid and a basic nitrogen compound to alumina gel or titania gel during the preparation of the carrier, or to use polyvinyl alcohol, polyethylene glycol, crystalline cellulose, etc. It is desirable to add an organic forming aid or an alcohol such as methyl alcohol, ethyl alcohol, or n-butyl alcohol.

The method of supporting the Group 6B metal and the Group 8 metal component on the carrier can also be carried out by a conventional method.

For example, the carrier may be immersed in a solution containing these hydrogenation-active metal components, the carrier may be mixed with this solution, the solution may be dropped onto the carrier, or hydrogenation may be carried out while the carrier is immersed in the solution. The hydrogenation-active metal component is supported on the carrier by contacting the carrier with a solution containing the hydrogenation-active metal component, such as by adding a precipitant for the active metal component and depositing the hydrogenation-active metal component on the carrier. method can be adopted.

Furthermore, the order of carrying Group 6B and Group 8 of the periodic table may be either first or at the same time.

Examples of molybdenum compounds that can be used as solutions of Group 6B metals of the periodic table include ammonium paramolybdate, molybdic acid, ammonium molybdate, and ammonium phosphomolybdate.

Examples of nickel compounds that can be used as solutions for Group 8 metals in the periodic table include phosphomolybdic acid, etc.
Nickel nitrates, sulfates, fluorides, chlorides, bromides, acetates, carbonates, phosphates, etc. Besides this,
Compounds of metals from Groups 6B and 8 of the Periodic Table known to those skilled in the art for use in this type of field may be used.

After the treatment as described above, it is preferable to perform drying, baking, etc. by a normal method.

Drying is usually done at room temperature to about 150°C, especially at about 100°C.
It is preferable to hold the temperature at ~120°C for about 5 hours or more, especially about 12 to 24 hours, and the firing is usually carried out at 34 room temperature to about 350 to 600°C, especially about 400 to 55°C.
Preferably, the temperature is maintained at 0°C for about 3 hours or more, especially about 12 to 24 hours.

Catalysts of the present invention typically contain about 7 to 25%, preferably about 10 to 20%, by weight of the Group 6B metal, calculated as oxides, and about 3 to 6%, preferably about 3% by weight, calculated as oxides. ~5
% by weight of Group 8 metals. It is considered that most of these hydrogenation-active metal components become oxides and some become simple elements in the above-mentioned fired catalyst.

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

As the sulfiding method, a method is employed in which hydrocarbon oil or gas phase sulfide containing about 1.0% by weight or more of sulfur is passed over a catalyst at high temperature and high pressure.

Table 1 shows the physical properties of the catalyst of the present invention detailed above.

Hydrocarbon oils that can be applied in the process of the present invention using the catalyst of the present invention include atmospheric distillate oils and residues of crude oil, vacuum distillate oils and residues, visbreaking oils, tar sand oils, and shale oils. Examples include oil.

In particular, the catalyst of the present invention is suitable for hydrogenating medium distillate oils such as kerosene fractions and gas oil fractions, heavy distillate oils from vacuum distillation, residual oils containing asphalt, or mixtures thereof. It is suitable for

Further, the hydrogenation treatment conditions in the method of the present invention include a temperature of about 2
00~450°C2 Pressure approximately 10~200Kg/cm2.
LH3V (liquid hourly hourly velocity) is preferably about 0.1 to 5, OHr'.

[Effect]

In the catalyst of the present invention, since the aluminum carrier contains silica and titania, silica atoms or titanium atoms and oxygen atoms chemically bond with the argonium atoms on the aluminum, creating new acidic points. , which improves the desulfurization activity of hydrogenation-active metals.

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

In addition, in the catalyst of the present invention, by strictly controlling the average pore diameter and pore distribution of the catalyst, it is possible to promote the diffusion of the target reactant into the catalyst, and to make it resistant to catalyst poisoning substances. Improves desulfurization activity.

In the method of the present invention, by using such a catalyst of the present invention in the hydrogenation treatment of hydrocarbon oil, the target substance in the hydrocarbon oil can be easily transferred into the catalyst on which a hydrogenation-active metal with high desulfurization activity is supported. In addition to highly efficient desulfurization, the deterioration of the catalyst activity of the present invention due to catalyst poisoning substances in the hydrocarbon oil is suppressed as much as possible.

In addition, "hydrotreatment" in the present invention refers to treatment by contacting hydrocarbon oil with hydrogen, and includes hydrorefining with relatively low severity of reaction conditions, and some decomposition reactions with relatively high severity of reaction conditions. These include hydrorefining, hydroisomerization, hydrodealkylation, and other reactions of hydrocarbon oils in the presence of hydrogen.

Examples include hydrodesulfurization, hydrodenitrogenation, and hydrocracking of distillates and residual oils from atmospheric distillation or vacuum distillation, and hydrorefining of kerosene fractions, gas oil fractions, waxes, and lubricating oil fractions. etc.

〔Example〕

Hereinafter, the present invention will be explained in more detail using Examples and Comparative Examples.

Example 1 200 g of aluminum-5ec-butoxide.

A solution of 8.64 g of titanium tetraisopropoxide and 16.42 g of tetraethoxysilane dissolved in isopropanol 4i is stirred at 80° C. for 1 hour.

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

The resulting slurry is filtered, heated and concentrated to form a plastic gel, and this gel is extruded into a bottom mold while adjusting the pressure to obtain the desired pore distribution, dried, and fired to form a catalyst. It was used as a carrier.

Weigh out 20g of this carrier and add 14.5mI! .

Add 4.7 g of ammonium molybdate dissolved in ion-exchanged water, soak for 1 hour, air dry, and heat at 500°C.
Roasted for 12 hours.

Next, 4.5 m of ion exchange water containing 5 g of cobalt nitrate
! ! was impregnated with, air-dried, and then burned 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 each contained in an amount of 5% by weight based on the weight of the carrier.

The specific surface area of this catalyst is 321 m2/g, and the pore volume is 0.
65 mj2/g, and the average pore diameter determined by mercury porosimeter injection method was 80.

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

Example 2 233 g of aluminum nitrate was dissolved in 609.0 mff1 of ion-exchanged water, and the aqueous solution was dissolved in 28 g while stirring.
% ammonia water and 600 ml of ion-exchanged water. At this time, the pH of the aqueous solution was maintained at 9 or more, and after being left as it was for 4 hours, the resulting suspension was passed through the mouth. The separated precipitate was aged in 800 mj2 of IN aqueous ammonium carbonate solution at 50°C for 12 hours, cooled, and passed through the mouth again.

After that, further 0.2% ammonia water 1.212. The mixture was washed with water and filtered to obtain a precipitate (■).

Separately, water glass (contains 3.8% silica by weight)
86g of ion exchange water 800+nI! , dissolved in
While stirring this aqueous solution, add a 5N sulfuric acid solution to pH 7.
It was gradually added dropwise until the concentration reached 5. After stirring for 2 hours, the resulting suspension was passed through the mouth. Pour the split sediment into 5 parts of ion-exchanged water! , 5 times to obtain a precipitate (■).

Furthermore, 110 g of 30% titanium nitrate solution was added to 6 liters of ion-exchanged water.
00 ml, and a 10% ammonia aqueous solution was added dropwise to this aqueous solution while stirring it until the pH reached 6. After stirring for 1 hour, the resulting suspension was passed through the mouth. The separated precipitate was washed 5 times with ion-exchanged water 31 to obtain precipitate (2).

The above precipitates (1) to (2) were mixed and thoroughly kneaded in a kneader. After that, the water content was adjusted, and extrusion molding was performed while adjusting the pressure to obtain the desired pore distribution. After air drying, 50"
A carrier was obtained by firing at C for 5 hours.

Weigh out 20g of the above carrier and add 12.5m! ! .

Add 4.7 g of ammonium molybdate dissolved in ion-exchanged water, soak for 1 hour, air dry, and heat at 450°C.
It was fired for 122 hours.

Next, 4.5 m of ion exchange water containing 5 g of Cobal nitrate)
It was impregnated with ff1, air-dried, and then calcined at 450°C for 122 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 are each 10% by weight based on the carrier weight,
It contained 5% by weight.

The specific surface area of this catalyst is 250 m2/g, and the pore volume is 0.
48rr+/2/g, and the average pore diameter determined by mercury porosimeter intrusion method 1 2 was 73 pieces.

Moreover, the volume occupied by 50 to 100 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 (contains 3.8% silica by weight)
Dissolve 167 g in 1000 m of ion-exchanged water, and add 5N sulfuric acid aqueous solution to pi-17 while stirring this aqueous solution.
, 5 gradually.

After stirring for 2 hours, the resulting suspension was passed through the mouth.

The split precipitate was washed five times with seven portions of ion-exchanged water to obtain a precipitate (■).

Furthermore, 21.1 g of 30% titanium sulfate solution was diluted with 200 mf of ion-exchanged water, and this aqueous solution was diluted with 10% titanium sulfate while stirring.
An ammonia aqueous solution was added dropwise until the pH reached 6. After stirring for 1 hour, the resulting suspension was passed through the mouth. The daily separated sediment was treated with ion-exchanged water II! , 5 times to obtain a precipitate (■).

The above precipitates (1) to (2) were mixed and thoroughly kneaded in a kneader. After that, the water content was adjusted and extrusion molding was performed while adjusting the pressure to obtain the desired pore distribution. After air drying, the
A carrier was obtained by firing at C for 5 hours.

Weigh out 20g of the above carrier and add 12.5mI! .

4.7 g of ammonium molybdate dissolved in ion-exchanged water was added, immersed for 1 hour, air-dried, and fired at 450° C. for 122 hours.

Next, 4.5 m of ion exchange water containing 5 g of nickel nitrate
After air drying, the catalyst was calcined at 450°C for 122 hours.

The resulting catalyst contained 4.7% by weight of nickel oxide and 14.8% by weight of molybdenum oxide. In addition, titania and silica are 2% by weight and 1% by weight, respectively, based on the carrier weight.
It contained 0% by weight.

The specific surface area of this catalyst is 301 m''/g, and the pore volume is 0.
52mff1/g, and the average pore diameter determined by mercury porosimeter intrusion method was 65.

Moreover, the volume occupied by 50 to 100 pores was 85% of the total pore volume (Catalyst C).

Comparative Example 1 3 4 The precipitate of Example 2 was prepared in exactly the same manner as in Example 2.

This was sufficiently kneaded using a kneader. Thereafter, the moisture content was adjusted and extrusion molding was carried out while adjusting the pressure to obtain the desired pore distribution. After air drying, it was calcined at 500''C for 5 hours to obtain a carrier.

20g of the above carrier was weighed out, and 4.7g of ammonium molybdate was dissolved in 12.5mf of ion-exchanged water.
was added, soaked for 1 hour, air-dried, and heated at 450°C for 12 hours.
Baked for an hour.

Next, 4°5 ion exchange water containing 5 g of cobalt nitrate was added.
ml was impregnated, air-dried, and then 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. Moreover, no substance other than Al was detected on the carrier.

The specific surface area of this catalyst is 260 m27 g, and the pore volume is 0.
59mff1/g, and the average pore diameter determined by mercury porosimeter intrusion method was 88 pieces.

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

Comparative Example 2 Precipitate (1) of Example 2 was prepared in exactly the same manner as in Example 2.

Separately, water glass (contains 3.8% silica by weight)
164g, ion-exchanged water 10100O.

While stirring this aqueous solution, a 5N sulfuric acid aqueous solution was gradually added dropwise until the pH reached 7.5.

After stirring for 2 hours, the resulting suspension was passed through the mouth.

The split precipitate was washed 5 times with ion-exchanged water 51 to obtain precipitate (2).

The precipitate (2) in Section 2 was mixed and thoroughly kneaded in a kneader. After that, the water content was adjusted, extrusion molding was performed while adjusting the pressure to obtain the desired pore distribution, and after air drying,
A carrier was obtained by calcining at °C for 5 hours.

4. Weighed 20g of the above carrier and dissolved it in 14.0mI2° ion-exchanged water.4.
7 g was added, immersed for 1 hour, air-dried, and baked at 5450°C for 12 hours.

Next, 4.5 r of ion exchange water containing 5 g of nickel nitrate
The catalyst was impregnated with r+p, air-dried, and then 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. Furthermore, 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 m27 g, and the pore volume is 0.
50rr+j2/g, and the average pore diameter determined by mercury porosimeter intrusion method was 61 pieces.

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

Comparative Example 3 Precipitate (1) of Example 2 was prepared in exactly the same manner as in Example 2.

Furthermore, 49 g of 30% titanium sulfate solution was added to 30 g of ion-exchanged water.
Dilute with 0 ml and add 10% while stirring this aqueous solution.
An ammonia aqueous solution was added dropwise until the pH reached 6. After stirring for 1 hour, the resulting suspension was passed through the mouth. Pour the split sediment into ion-exchanged water 21
The mixture was washed five times with water to obtain a precipitate (■).

2 parts of the precipitate obtained in Section 2 were combined and thoroughly kneaded in a kneader. After that, the water content was adjusted, extrusion molding was performed while adjusting the pressure to obtain the desired pore distribution, and after air drying,
A carrier was obtained by calcining at °C for 5 hours.

Weigh out 20g of the above carrier and apply 13.0mp to it.

Add 4.7 g of ammonium molybdate dissolved in ion-exchanged water, soak for 1 hour, air dry, and heat at 450°C.
It was baked for 12 hours.

Next, 4.5 m of ion exchange water containing 5 g of Cobal nitrate)
ff was impregnated, air-dried, and then 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 m2/g, and the pore volume is 0.
The average pore diameter determined by mercury porosimeter injection method 7 8 was 51 mff/g.

Moreover, the volume occupied by 50 to 100 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.

Apart from this, water glass (containing 93.8% by weight of silica)
491 g was dissolved in ion-exchanged water, and while stirring this aqueous solution, a 5N sulfuric acid aqueous solution was gradually added dropwise until the pH reached 7.5. After stirring for 2 hours, the resulting suspension was passed through the mouth.

The separated precipitate was washed five times with 10ffi of ion-exchanged water to obtain a precipitate (2).

Furthermore, 310g of 30% titanium sulfate solution was added to 110g of ion-exchanged water.
．． 51, and a 10% ammonia aqueous solution was added dropwise to this aqueous solution while stirring it until the pH reached 6. As is 1
After stirring for an hour, the resulting suspension was sipped. The separated precipitate was washed five times with 81 portions of ion-exchanged water to obtain a precipitate (2).

The above precipitates (1) to (2) were mixed and thoroughly kneaded in a kneader. After that, the water content was adjusted, and extrusion molding was performed while adjusting the pressure to obtain the desired pore distribution. After air drying, 50"
A carrier was obtained by firing at C for 5 hours.

Weigh out 20g of the above carrier and add 12.0mI! .

Add 4.7 g of ammonium molybdate dissolved in ion-exchanged water, soak for 1 hour, air dry, and heat at 450°C.
It was fired for 122 hours.

Next, 4.5 m of ion exchange water containing 5 g of Cobal nitrate)
j2 was impregnated, air-dried, and then calcined at 450°C for 122 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 2% by weight, respectively, based on the carrier weight.
It contained 0% by weight.

The specific surface area of this catalyst is 163 m2/g, and the pore volume is 0.
39mj! /g, and the average pore diameter determined by mercury porosimeter intrusion method was 88λ.

Moreover, the volume occupied by 50 to 100 pores was 62% of the total pore volume (Catalyst G).

9 Comparative Example 5 Precipitates ① to ② of Example 2 were prepared in exactly the same manner as in Example 2.

Each precipitate was first spray-dried and calcined, then water was added again to adjust the humidity, and the mixture was sufficiently kneaded in a kneader. Thereafter, extrusion molding was carried out while adjusting the pressure to obtain a desired pore distribution, and after air drying, the carrier was calcined at 500°C for 5 hours to obtain a carrier.

Weighed 20g of the above carrier and added ammonium molybdate 4 dissolved in 12.5rr+42 ion exchange water.
．． 7 g was added, immersed for 1 hour, air-dried, and baked at 450°C for 122 hours.

Next, 4.5 m of ion exchange water containing 5 g of cobalt nitrate
ff1 was impregnated, air-dried, and then calcined at 450°C for 122 hours to obtain a catalyst.

The resulting catalyst contained 4.7% by weight of cobalt oxide and 14.8% by weight of molybdenum oxide. In addition, titania and silica are 10% by weight and 5% by weight, respectively, based on the carrier weight.
Contained by weight%.

The specific surface area of this catalyst is 185 m2/g, the pore volume is 0, and the pore area is 0, 53 m41! /g, and the average pore diameter determined by mercury porosimeter injection method was 120.

Moreover, the volume occupied by 50 to 100 pores was 35% of the total pore volume (Catalyst H).

Catalyst A prepared in Examples 1-3 and Comparative Examples 1-5 above
The physical properties of -H are shown in Table 2.

1 2 33 In addition, the catalysts A to H obtained in Examples 1 to 3 and Comparative Examples 1 to 3 above were evaluated in a hydrodesulfurization relative activity evaluation test under the following conditions.

Arabian light gas oil (LG○), vacuum gas oil (VGO)
Alternatively, the relative activity of hydrodesulfurization for Arabian Heavy atmospheric residual extraction (AH-AR) was measured on the 10th day (condition 1) and the 20th day (condition 2) using a fixed bed reaction tube with an inner diameter of 10 mmφ.
, 25th day (Condition 3) (At the beginning of the reaction, the sulfur content of the product is small, but it increases and stabilizes as the days pass, so on the 10th day,
It was set as the 20th day and the 25th day. ) The initial relative desulfurization activity obtained from the residual sulfur content (wt%) of the reaction product was determined.

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

4 It can be seen that compared to Comparative Examples 6 to 10 using catalysts DH of Examples 1 to 5, excellent results were shown in the desulfurization activity of light gas oil.

Table 5 Note 1) Relative value of desulfurization reaction rate constant of Comparative Example 6 expressed as 100. Values in parentheses indicate the sulfur concentration of the produced oil (wt%).

As is clear from Table 4, catalysts A-C of Examples 1 to 3
Comparability 2) Comparative Example 1
Relative value expressed as 100 for the desulfurization reaction rate constant of 1. Values in parentheses indicate the sulfur concentration of the produced oil (wt%).

7 As is clear from Table 5, catalysts A to C of Examples 1 to 3
All of Examples 7 to 9 used were catalysts D of Comparative Examples 1 to 4.
It can be seen that compared to Comparative Examples 11 to 14 using -G, excellent results were shown in the desulfurization activity of vacuum gas oil.

Both Examples 10 and 1.1 using the sixth surfactants A and B have better desulfurization of atmospheric residual oil than Comparative Examples 1 and 5 using catalysts 15 and 16 using H. It can be seen that the results show excellent activity.

〔Effect of the invention〕

In the catalyst of the present invention, acidic points that are convenient for desulfurization of hydrocarbon oil are newly formed, and furthermore, the target reactant can diffuse well inside the catalyst, and it has excellent resistance to catalyst poisoning substances. , the desulfurization activity of hydrocarbon oil has been significantly 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, compared to the conventional hydrorefining method for hydrocarbon oil, it is possible to It can also desulfurize oil with high efficiency, and is particularly effective for petroleum distillate raw materials.

Note 3) Relative value of the desulfurization reaction rate constant of Comparative Example 15 expressed as 100. Values in parentheses indicate the sulfur concentration of the produced oil (wt%).

As is clear from Table 6, the distributor of patents in Examples 1 and 2: Cosmo Oil Co., Ltd., Cosmo Research Institute Co., Ltd. 9

Claims (1)

[Scope of Claims] (1) A catalyst carrier consisting of alumina, silica, and titania contains at least one metal selected from Group 6B of the Periodic Table as a catalytically active component of 7 to 25% in terms of oxide based on the catalyst. 3 to 6% by weight, and at least one metal selected from Group 8 of the Periodic Table in terms of oxide based on the catalyst.
The silica and titania in the catalyst carrier are each 1 to 10% by weight based on the carrier, and the pore characteristics of the catalyst are: (1) average pore size measured by mercury porosimeter injection method; (2) the volume occupied by pores with an average pore diameter of 50 to 100 Å is at least 50% of the total pore volume; (3) the specific surface area is at least 150 m^2/g; (4)
A catalyst composition for hydrotreating hydrocarbon oil, characterized in that the total pore volume is 0.4 to 1.5 ml/g. (2) A method for hydrodesulfurization of hydrocarbon oil, characterized in that the catalyst composition according to item 1 is used.