JPH07136516A - Production of catalyst for hydrogenating, desulfurizing and denitrifying hydrocarbonaceous oil - Google Patents

Abstract

PURPOSE:To eliminate the defects of the conventional hydrocarbon oil hydrogenation catalyst and provide a catalyst capable of efficiently hydrogenating, desulfurizing and denitrifying the hydrocarbonaceous oil. CONSTITUTION:An oxide carrier consisting essentially of boriasilica-alumina is impregnated with an.aq. metallic salt soln. contg. 17-28wt.% of at least one kind of metal selected from group VIa metals, expressed in terms of the oxide, and 3-8wt.% of at least one kind selected from group VIII metals, expressed in terms of the oxide, as active metal components and then dried.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a hydrotreating catalyst for effectively removing both sulfur compounds and nitrogen compounds contained in a hydrocarbon oil. More specifically, in order to reduce the content of sulfur and nitrogen in the raw hydrocarbon oil at the same time by treating a hydrocarbon oil containing a large amount of sulfur compounds, especially nitrogen compounds, under hydrogen pressure and converting it into hydrogen sulfide and ammonia. The present invention relates to a method for producing a hydrotreating catalyst used in.

[0002]

2. Description of the Related Art A conventional hydrotreating catalyst mainly composed of hydrodesulfurization is composed of a porous alumina-based catalyst carrier,
A catalyst supporting a Group 6a metal and a Group 8 metal of the periodic table is generally used. However, these hydrotreating catalysts reduce the amount of hydrogen consumed when the hydrodesulfurization reaction is performed and show high activity for the hydrodesulfurization reaction, but sufficient activity for the hydrodenitrogenation reaction. Not shown. On the other hand, from gasoline, kerosene, and light oil (boiling point about 340 ° C), the remaining hydrocarbon oil, which is generally called residual oil, is used to produce fuel oil through a hydrodesulfurization process. Fuel oil with less consumption is desired.

By the way, in order to treat a hydrocarbon oil to simultaneously remove a sulfur compound and a nitrogen compound, in addition to the conventionally known hydrodesulfurization activity, a hydrodenitrogenation activity for cleaving a C--N bond is also used. A catalyst equipped with is required.

Various studies have been carried out as a catalyst having both hydrodesulfurization and denitrification activities. For example, US Pat. No. 3,446,730 discloses 1.2 to 2.6 of water of crystallization. Nickel or Group 6 metals or oxides or sulfides of these metals are supported on an alumina carrier prepared by firing aluminum hydroxide contained therein, and further 0.1 to 2.6.
A catalyst with a promoter consisting of wt.% Phosphorus, silicon or barium has been proposed, but no mention is made of the properties of the support. Moreover, it is described that the treated oil can be applied to any distillate including the residual oil, but it is clear that only the distillate oil is actually targeted.

Further, US Pat. No. 3,749,664 describes a catalyst in which molyfden, nickel and phosphorus are supported on an alumina or silica-alumina carrier in a specific ratio, and the carrier is generally 0. Although it is described that those having a pore volume of 0.6 to 1.4 cc / g are preferable,
The pore structure has not been studied at all, and it does not have satisfactory performance for hydrotreating hydrocarbons.

As an improvement of the above, Japanese Laid-Open Patent Publication No. 56-40432
The publication discloses titanium oxide as a carrier on which a metal of Group 6 and a metal of Group 8 of the Periodic Table and phosphorus or boron are similarly supported as a catalyst component. However, titanium oxide used as a carrier is The price is high, and it is difficult to increase the specific surface area compared to alumina due to its physical properties. Moreover, the specific surface area tends to decrease during calcination after supporting the catalyst component. Difficult to maintain in range.

As described above, in any of the catalysts, an active metal belonging to Groups 6a and 8 of the Periodic Table as a catalyst component is also loaded with phosphorus or the like, which has a catalytic promoting effect, on the acid point of the catalyst. However, even if phosphorus is evenly supported on the catalyst, if the catalyst is left in the atmosphere, phosphorus will absorb moisture and the supported state will change.

Generally, a method for producing a hydrotreating catalyst for hydrocarbon oils comprises the steps of impregnating an inorganic oxide carrier with an aqueous solution of an active metal, drying, and then calcining. No attempt has been made to impregnate such a carrier with an aqueous solution of an active metal and then to dry it, and apply the dried product as it is as a hydrotreating catalyst.

[0009]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention The inventors of the present invention have previously improved the carrier for the purpose of increasing the acid point of the carrier that is the base of the catalyst, and as a result, have the carrier composed of the boria-silica-alumina composition. Was found and the performance of a catalyst in which a metal of Group 6a of the periodic table and a metal of Group 8 of the periodic table were carried on the carrier was examined, and the performance of the catalyst was confirmed. In order to satisfy both reactions at the same time, it was found that there is a preferred specific range for the composition ratio and the pore size in the carrier boria-silica-alumina composition, and there is also a suitable range for the amount of supported metal, A patent application was filed for this, and the present invention was reached as a result of further intensive research to improve both hydrodesulfurization and denitrification activities.

That is, the present invention solves the problems of the conventional hydrocarbon oil hydrogenation catalysts as described above, and is sufficiently equipped with both hydrodesulfurization and denitrification activities of hydrocarbon oils.
Moreover, it is an object of the present invention to provide a method for producing a catalyst for hydrodesulfurization and denitrification, in which the steps are simplified.

[0011]

Means for Solving the Problems The present invention for achieving the above object is selected from metals of Group 6a of the periodic table as an active metal component for an oxide carrier based on boria-silica-alumina. An aqueous metal salt solution containing 17 to 28% by weight of at least one metal in terms of oxide and 3 to 8% by weight in terms of oxide of at least one metal selected from Group 8 metals of the periodic table. A method for producing a catalyst for hydrodesulfurization and denitrification of hydrocarbon oil, which comprises impregnating and drying.

In the present invention, the composition of the oxide carrier based on boria-silica-alumina is 3 to ₃ as B ₂ O 3.
The range is 10% by weight, and 3 to 8% by weight as SiO _2.
And the pore characteristics of the oxide support have an average pore diameter of 60 to 90 angstrom in terms of pore distribution measured by mercury porosimetry, and an average pore diameter of ± 10 angstrom. It is preferable that the pore volume in the range is at least 60% of the total pore volume.

As the catalytically active component to be supported, at least one selected from the metals of Group 6a of the periodic table and at least one selected from the metals of Group 8 of the Periodic Table are supported within the above-mentioned content range. It is necessary to impregnate these active metal salt aqueous solutions and dry them in order to support these active metals. The obtained catalyst in a dried state can be subjected to the same sulfurization treatment as a generally used method before being subjected to the hydrotreating treatment before being used.

[0014]

The operation of the present invention will be described in detail below. The carrier of the present invention comprises a boria-silica-alumina composition having a composition in the range of ₃ to 10% by weight as B ₂ O ₃ , 3 to 8% by weight as SiO ₂ , and the balance Al ₂ O _3. Otherwise, no dramatic improvement in denitrification activity will be observed. It is considered that this improvement in activity is due to the synergistic effect of the above three components of the carrier.

The metals used as Group 6a metals of the periodic table are chromium, molybdenum and tungsten, and of these, particularly preferred is molybdenum. Further, those used as the Group 8 metal of the periodic table are iron, cobalt, and nickel, and particularly preferable among these are nickel and / or cobalt. Both Group 8 metals are used in appropriate combination. The content of the active metal is 17 to 28% by weight based on the total amount of the catalyst in terms of oxide for Group 6a metal in the periodic table, and 3 to 8% by weight in terms of oxide for Group 8 metal in the periodic table. Is. And the lower limit of these metal components shows the minimum necessary for the desired generation of hydrodesulfurization, denitrification activity, above the upper limit, even if added in an amount more than this, hydrodesulfurization, denitrification activity of No increase is observed.

With respect to the pore diameter and the pore distribution of the catalyst carrier based on boria-silica-alumina, the number of pores having a pore diameter effective for desulfurization and denitrification should be increased as much as possible.
In order to suppress other harmful reactions, a dry catalyst obtained when the pore distribution is narrow and the volume occupied by pores having an average pore diameter of ± 10 Å is at least 60% or more of the total pore volume. The effect of desulfurization and denitrification is most excellent.

If the average pore size of the boria-silica-alumina carrier is smaller than this, the diffusion resistance of the reactant within the catalyst particles is large, and both hydrodesulfurization and denitrification activities are reduced. Further, even if the average pore size of the boria-silica-alumina carrier falls within the range of 60 to 90 angstroms, when the volume occupied by the pores of the average small diameter ± 10 angstrom is less than 60% of the total pore volume, Both pores effective for hydrodesulfurization and denitrification of hydrocarbon oil are reduced, and both activities are reduced.

The carrier based on boria-silica-alumina having a narrow pore distribution and an average pore diameter within a predetermined range as described above can be manufactured by a general catalyst carrier manufacturing method such as a mixing method. Alumina hydrate slurry produced by mixing an aqueous solution of aluminum sulfate and sodium aluminate and hydrolyzing the mixture has a silica content of 3 to 8 wt% as SiO ₂ when used as a catalyst carrier.
Become so by adding sodium silicate solution 0.05, filtered, by performing washing, as Na 2 _O
% Silica, and a silica-alumina catalyst containing 0.20% by weight of SO ₄ is obtained, and when the hydrate is used as a carrier, the boria content is 3-10% by weight as B ₂ O _3. By adding an aqueous acid solution and kneading until the water content becomes moldable, molding into a general catalyst carrier shape such as cylindrical, spherical, three-leaf type, four-leaf type, etc., then drying and then firing It can be manufactured.

It should be noted that the addition of an organic acid such as gluconic acid or tartaric acid during the hydrolysis reaction for obtaining the alumina hydrate is effective for obtaining a catalyst having a pore distribution concentrated in a specific range. is there.

Further, as the boria raw material used for producing the boria-silica-alumina composition,
For example, water-soluble salts of boric acid, tetraboric acid and the like,
Examples of the silica raw material include water-soluble salts such as sodium silicate and silicon tetrachloride, and examples of the alumina raw material include aluminum nitrate, aluminum sulfate, aluminum chloride, sodium aluminate and the like, and water-soluble salts thereof. Is mentioned.

To support the active metal component on the boria-silica-alumina-based carrier having the desired pore structure thus obtained, for example, molybdenum trioxide, nickel carbonate, and cobalt carbonate are added to water. An organic acid such as citric acid or tartaric acid was added to the slurry suspended in to prepare an aqueous solution that was heated and dissolved.
Silica-alumina carrier is impregnated to absorb the liquid, and the concentration of the aqueous solution is adjusted so that a desired amount of active metal component can be supported, or the desired active metal is dissolved and the total amount of the aqueous solution is adsorbed. Then, the catalyst of the present invention can be obtained by drying.

In the conventional catalyst manufacturing process, the catalyst is obtained by impregnating the carrier with the active metal salt aqueous solution, then drying and calcining. In the manufacturing method of the present invention, the catalyst is calcined during the manufacturing process. It is also advantageous in terms of thermal energy because it eliminates the need for steps. The catalyst obtained by the production method of the present invention is a catalyst obtained by the conventional catalyst production method of impregnating an oxide support with an active metal in a hydrodesulfurization and denitrification reaction of hydrocarbon oil, followed by drying and calcination. On the other hand, it shows remarkably superior activity as compared with the one subjected to sulfurization treatment.
Although the reason for this is not clear, since the active metal component contained in the catalyst obtained by the final calcination in the prior art is in an oxide state, the active metal component such as molybdenum sulfide produced in the step of sulfurization treatment is not formed. It is considered that the activity is inferior to that according to the present invention because the particle size is smaller than that according to the present invention and is in a highly dispersed state.

[0023]

EXAMPLES Next, examples of the present invention will be described. (1) Production of Catalyst Carrier Example 1 204 g (hydrolysis) of gluconic acid solution (manufactured by Wako Pure Chemical Industries, Ltd.) having a content of 49.5 liters of water and a concentration of 50% was placed in a stainless steel reactor having an internal volume of 100 liters equipped with a stirrer. 0.05 wt% with respect to Al ₂ O ₃ produced by the above) was put in a reaction tank, and the mixture was heated and maintained at 70 ° C. and stirred while Al ₂ O ₃ was added.
Aluminum sulfate aqueous solution containing 774 g as
9540g of 8% sulfuric acid band sold by Shimada Shoten, and Al ₂
6930 g of a sodium aluminate aqueous solution (NA-170 manufactured by Sumitomo Chemical Co., Ltd.) containing 1275 g as O ₃ was mixed to obtain an alumina hydrate slurry having a pH of 9.0. Next, after aging this slurry for 30 minutes, a concentration of 31
% Nitric acid 25 g to bring the pH to 8.3, then Si
A total of 929 g of an aqueous sodium silicate solution (manufactured by Ko Pure Chemical Industries, Ltd.) containing 130 g as O ₂ was added dropwise to obtain a silica-alumina hydrate having a pH of 8.8. After aging this hydrate for 30 minutes, it was filtered and washed to obtain 2500 g of a silica-alumina hydrate cake (SiO ₂ -Al ₂
O ₃ of 20% by weight of the total composition) boric acid (Wako Pure Chemical Industries, Ltd. and manufactured) 47 g _(26.6 g as B 2 _{O 3)} was added and heated kneading in a heating jacketed kneader, B
63% by weight of a plastic knead as a concentration of ₂ O ₃ —SiO ₂ —Al ₂ O ₃ was obtained, and the kneaded product was then given a diameter of 1.
A boria-silica-alumina carrier containing 5% by weight of B ₂ O _{3 and} 5.7% by weight as SiO ₂ after being molded by an extruder having a 5 mmφ die, dried, and fired at 700 ° C. for 2 hours in an electric furnace. I got A. Example 2 Except for changing the addition amount of boric acid added to the silica-alumina hydrate obtained in Example 1, 3% by weight as B ₂ O ₃ was prepared in substantially the same manner as in Example 1. , SiO ₂
Boria containing 5.8% by weight - silica - alumina support B and _B 2 _{O 3} as a 10 wt%, 5 as SiO _2.
A boria-silica-alumina carrier C containing 4% by weight was obtained. Example 3 The amount of the sodium silicate aqueous solution added to the alumina hydrate slurry obtained in substantially the same manner as in Example 1 was changed to Si.
5% by weight of B ₂ O ₃ was added in the same manner as in Example 1 except that O ₂ was 3% by weight and 8.5% by weight, respectively, and SiO _{2 was} 2.9% by weight and B ₂ O ₃ was added. Boria-silica-alumina support D and SiO containing 5% by weight
_{2 8.1%, B 2 O 3} 5 % by weight of the total composition boria - silica -
Alumina carrier E was obtained.

Carriers A, B obtained in Examples 1, 2 and 3,
When the pore structures of C, D and E were measured by the mercury porosimetry, the average pore diameters were all in the range of 65 ± 5 Å, and the volume occupied by the average pore diameter ± 10 Å was occupied by all the pores. It occupied over 60% of the volume. Comparative Example 1 Alumina hydrate cake 2 obtained by filtering and washing the alumina hydrate slurry obtained in substantially the same manner as in Example 1
Kneading 500 g in a kneader with a heating jacket to obtain a kneaded product having a plasticity of 60% by weight as an Al ₂ O ₃ concentration, and then the kneaded product was extruded with a die having a diameter of 1.5 mmφ. Molded in, dried and 500 in an electric furnace
Alumina carrier F was obtained by firing for 2 hours at ℃.

As a result of measuring the pore structure of the obtained carrier F by the mercury penetration method, the average pore diameter is 70 Å, and the volume occupied by the pores in the range of average pore diameter ± 10 Å is occupied by all the pores. It was 61% of the volume. Comparative Example 2 2500 g of a silica-alumina hydrate cake obtained in substantially the same manner as in Example 1 was heat-kneaded in a kneader with a heating jacket to give a 62% by weight plasticity of SiO ₂ —Al ₂ O ₃ concentration of 62% by weight. A certain kneaded product is obtained, and then this kneaded product is molded with an extruder having a die with a diameter of 1.5 mmφ,
After drying, it was baked in an electric furnace at 700 ° C. for 2 hours to obtain a silica-alumina carrier G containing 6% by weight as SiO ₂ .

As a result of measuring the pore structure of the obtained carrier G by mercury porosimetry, the average pore diameter is 71 Å, and the volume occupied by the pores in the range of average pore diameter ± 10 Å is occupied by all the pores. It was 63% of the volume. Comparative Example 3 5% by weight of B ₂ O ₃ and Si were prepared by the same procedure as in Example 1 except that gluconic acid was not added to the reaction tank.
A boria-silica-alumina carrier H containing 5.7% by weight of O ₂ was obtained.

As a result of measuring the pore structure of the obtained carrier H by mercury porosimetry, the average pore diameter is 69 Å, and the volume occupied by the pores in the range of average pore diameter ± 10 Å is occupied by all the pores. It was 48% of the volume.

Prepared in Examples 1-3 and Comparative Examples 1-3
Structure measured by mercury porosimetry for different carriers
The values for are shown in Tables 1 and 2.(2) Preparation of catalyst  Example 4 23.4 g of molybdenum trioxide, 11.8 g of nickel carbonate
Is suspended in 50 g of water, 2.0 g of tartaric acid is added, and the mixture is heated.
Dissolve with water and adjust the liquid volume with water to match the water absorption of the carrier.
The impregnating liquids obtained were obtained in Example 1, Example 2 and Example 3.
The average pore diameter within the range of the present invention
The volume occupied by pores in the ngstrom range is the total pore volume.
Boria-Si having a pore structure of 60% or more of
Rica-alumina carrier A, B, C, D and E 100 each
g and impregnate it for 2 hours, then dry at 110 ° C for 16 hours
And then calcined at 500 ° C. for 2 hours to obtain catalysts I, J, K,
L and M were obtained. Comparative Example 4 Carrier F obtained in Comparative Example 1, Comparative Example 2 and Comparative Example 3
(Alumina carrier), simple substance G (silica-alumina carrier) or
And a carrier H (having a pore structure outside the scope of the present invention)
(Boria-silica-alumina carrier)
Catalysts N, O and P were obtained in a procedure similar to that in Example 4. Example 5 Molybdenum trioxide 39.7 g, nickel carbonate 13.4 g
Is suspended in 50 g of water, 2.0 g of tartaric acid is added, and the mixture is heated.
Dissolve with water and adjust the liquid volume with water to match the water absorption of the carrier.
The impregnating solution used was the boria-silica-aluminum obtained in Example 1.
Impregnate 100 g of carrier A and leave for 2 hours at 110 ° C
After drying for 16 hours, catalyst Q was obtained.

Further, 23.4 g of molybdenum trioxide and 16.5 g of nickel carbonate were suspended in 50 g of water to obtain 2.0 g of tartaric acid.
Was added and dissolved under heating, and the impregnating liquid in which the liquid amount was adjusted to a liquid amount corresponding to the water absorption amount of the carrier was impregnated with 100 g of the boria-silica-alumina carrier A obtained in Example 1 and the resulting solution was used for 2 hours. After standing, it was dried at 110 ° C. for 16 hours and then calcined at 500 ° C. for 2 hours to obtain a catalyst R. Example 6 39.7 g of molybdenum trioxide, 12.2 g of cobalt carbonate
Was suspended in 50 g of water, 2.0 g of tartaric acid was added and dissolved under heating, and the impregnating liquid obtained by adjusting the liquid amount with water to a liquid amount corresponding to the water absorption amount of the carrier was obtained in Example 1. -Alumina simple substance A (100 g) was impregnated, left for 2 hours, dried at 110 ° C for 16 hours, and then calcined at 500 ° C for 2 hours to obtain a catalyst S.

Further, 23.4 g of molybdenum trioxide and 15.1 g of cobalt carbonate were suspended in 50 g of water to obtain 2.0 g of tartaric acid.
Was added and dissolved under heating, and the impregnating liquid in which the liquid amount was adjusted to a liquid amount corresponding to the water absorption amount of the carrier was impregnated with 100 g of the boria-silica-alumina carrier A obtained in Example 1 and the resulting solution was used for 2 hours After standing, it was dried at 110 ° C. for 16 hours and then calcined at 500 ° C. for 2 hours to obtain a catalyst T. Comparative Example 5 An impregnation liquid was prepared by suspending 14.0 g of molybdenum trioxide and 4.2 g of nickel carbonate in 50 g of water, dissolving them under heating, and adjusting the liquid volume with water to a liquid volume corresponding to the water absorption of the carrier. 100 g of the boria-silica-alumina carrier A obtained in 1 was impregnated, left to stand for 2 hours, dried at 110 ° C. for 16 hours, and then 5
A catalyst U was obtained by calcining at 00 ° C. for 2 hours.

In this catalyst U, the supported amounts converted to MoO ₃ and NiO were both less than the range of the present invention. Comparative Example 6 Molybdenum trioxide 24.7 g, nickel carbonate 12.2 g
Was suspended in 50 g of water, 8.9 g of orthophosphoric acid was added and dissolved under heating, and the impregnating liquid obtained by adjusting the liquid amount with water to a liquid amount corresponding to the water absorption amount of the carrier was obtained in Example 1. -Silica-alumina carrier A, alumina carrier F obtained in Comparative Example 1 and silica-alumina carrier G obtained in Comparative Example 2 were each impregnated with 100 g of each, allowed to stand for 2 hours, dried at 110 ° C for 16 hours, and then 500 The catalyst was calcined at 2 ° C. for 2 hours to obtain catalyst V, catalyst W and catalyst X. All of these catalysts contain phosphorus and are outside the scope of this invention. (3) Catalyst Performance Evaluation Test For each of the catalysts shown in Tables 1 and 2, the activity of hydrodesulfurization and denitrification of hydrocarbon oil was investigated using a fixed bed flow reactor with a catalyst loading of 15 ml.

The catalyst sulfurization conditions were light gas oil containing 2.5% by weight of dimethyldisulfide, hydrogen / oil supply ratio of 200 Nl / l, LHSV = 2.0 hr.
The temperature was raised from 100 ° C. to 315 ° C. over 7 hours under the conditions of ⁻¹ and a pressure of 30 kg / cm ² G, and the temperature was maintained for 16 hours for pre-sulfurization.

Next, the sulfur content is 1.15% by weight and the nitrogen content is 6
Using Kuwait atmospheric gas oil containing 8ppm, pressure 30kg
/ Cm ² G, LHSV = 2.0 hr ⁻¹ , hydrogen / oil supply ratio 300 Nl / l, temperature 300 ° C., the reaction was carried out, and the sulfur content and nitrogen content in the treated oil 100 hours after the reaction start were analyzed. Then, the desulfurization rate and the denitrification rate were calculated and the results are shown in Table 1.
It was shown to.

Sulfur content was analyzed by SLF manufactured by Horiba Ltd.
The A-920 model was used, and the nitrogen content was analyzed using a TN-05 model manufactured by Mitsubishi Kasei. Table 1
The desulfurization rate and denitrification rate shown in Table 2 are 10
It is a relative value when 0 is set.

The desulfurization rate and denitrification rate of the catalyst W shown in Table 2 are set to 100 because the catalyst W is prepared by a conventional method for producing a hydrotreating catalyst, and is generally hydrodesulfurization and denitrification. This is because it has almost the same properties as a commercially available catalyst in which MoO ₃ , NiO and P ₂ O ₆ are supported on a carrier based on alumina as a catalyst showing activity.

[0036]

[Table 1]

[Table 2]

In the results of each table, the catalyst I, the catalyst J, the catalyst K, the catalyst L and the catalyst M in Table 1 have the same molybdenum and nickel contents in terms of oxide, and the carrier boria-silica-alumina. The composition ratio, the average pore size and the pore distribution of the composition, and the amount of the active metal supported are all catalysts that satisfy the ranges defined in the present invention, and exhibit high desulfurization rate and denitrification rate. Is clear.
On the other hand, in the catalyst P, the amount of active metal supported and the composition ratio of the boria-silica-alumina carrier belong to the ranges defined in the present invention, but the average pore diameter of the carrier is ± 10 angstrom pore volume / total pore volume (% ) Value remains at 48% and the distribution of pores is wide, the desulfurization rate and denitrification rate of this catalyst P are
The value is lower than that of catalyst I having a narrow pore distribution.

The catalyst N and the catalyst O are within the ranges defined in the present invention with respect to the amount of the active metal supported, the average pore size and the pore distribution, but the carrier component does not contain boria and / or silica. Therefore, although the desulfurization rate shows a satisfactory value, the denitrification rate shows a low value.

Further, catalyst Q, catalyst R and catalyst U in Table 2
Satisfies the range of the present invention with respect to the composition ratio of the boria-silica-alumina carrier, the average pore diameter and the pore distribution, but regarding the supported amounts of molybdenum and nickel in terms of oxide, the catalyst I is It has been changed. That is, the catalyst Q has molybdenum added more than the catalyst I, and the catalyst R has nickel added more than the catalyst I.
All of them are within the scope of the present invention and exhibit sufficiently high desulfurization rate and denitrification rate. However, the catalyst U has a reduced amount of molybdenum and nickel as compared with the catalyst I, and since the content thereof is outside the range of the present invention, both the desulfurization rate and the denitrification rate show low values.

The catalyst S and the catalyst T are boria-silica-
The composition ratio of the alumina carrier, the average pore diameter and the pore distribution belong to the scope of the present invention, and cobalt instead of nickel as the active metal is supported in an amount within the scope of the present invention, It shows high desulfurization and denitrification rates.

The catalyst V is within the scope of the present invention in terms of the composition ratio of boria-silica-alumina carrier, average pore diameter and pore distribution, but it supports phosphorus in addition to molybdenum and nickel as active metals. Therefore, the desulfurization rate and the denitrification rate are lower than those of the catalyst W. This is usually carried out by adding phosphorus as a co-catalyst to improve desulfurization and denitrification activities when the acid point of the carrier is low, but the carrier based on boria-silica-alumina of the present invention is Basically, the acid point is higher than that of a commonly used alumina-based carrier, and therefore, when phosphorus is supported, the acid point becomes too high and the desulfurization rate and denitrification rate are rather lowered.

The catalyst X is a simple substance of silica-alumina on which molybdenum and nickel are supported as active metals, respectively, and the average pore diameter and the pore distribution are within the range defined by the present invention. When compared with the catalyst, the desulfurization and denitrification activities are slightly improved, but the values are lower than those of the catalyst I of the present invention.

[0043]

The catalyst for hydrodesulfurization and denitrification of hydrocarbon oil obtained by the production method of the present invention desulfurizes and denitrifies much more efficiently than conventionally proposed catalysts of this type. be able to. Therefore, by using the catalyst of the present invention in place of the conventional catalyst, it becomes possible to obtain a fuel oil having a low sulfur content and a low nitrogen content.

Claims (3)

[Claims] 1. An oxide carrier based on boria-silica-alumina containing at least one metal selected from metals of Group 6a of the periodic table as an active metal component in an amount of 17 to 28% by weight in terms of oxide. Hydrogenating a hydrocarbon oil comprising impregnating an aqueous metal salt solution containing at least one metal selected from Group 8 metals of the Periodic Table with 3 to 8% by weight in terms of oxide and drying. A method for producing a catalyst for desulfurization and denitrification. 2. The composition of the oxide carrier based on boria-silica-alumina is in the range of ₃ to 10 wt% as B ₂ O ₃ and in the range of 3 to 8 wt% as SiO _2. The pore characteristics of the oxide carrier have an average pore diameter of 60 to 90 angstrom in the pore distribution measured by the mercury porosimetry method, and the pore volume in the range of the average pore diameter ± 10 angstrom is the total pore volume. The method for producing a catalyst for hydrodesulfurization and denitrification of hydrocarbon oil according to claim 1, wherein the catalyst is 60% or more. 3. The active metal component is represented by Periodic Table 6a.
The method for producing a catalyst for hydrodesulfurization and denitrification of hydrocarbon oil according to claim 1, wherein the group metal is molybdenum, and the group 8 metal of the periodic table is at least one of nickel and cobalt. .