JP2920186B2 - Method for producing catalyst for hydrodesulfurization and denitrification of hydrocarbon oil - Google Patents

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, a hydrocarbon oil containing a large amount of sulfur compounds, particularly nitrogen compounds, is treated under hydrogen pressure to convert it into hydrogen sulfide and ammonia, thereby simultaneously reducing the sulfur and nitrogen contents in the raw hydrocarbon oil. The present invention relates to a method for producing a hydrotreating catalyst used in the above.

[0002]

2. Description of the Related Art Conventional hydrotreating catalysts mainly based on hydrodesulfurization include a catalyst support having porous alumina as a base material.
Catalysts supporting a Group 6a metal and a Group 8 metal on the periodic table are generally used. However, these hydrotreating catalysts reduce the amount of hydrogen consumed during the hydrodesulfurization reaction and exhibit high activity for the hydrodesulfurization reaction, but have sufficient activity for the hydrodenitrogenation reaction. Not shown. On the other hand, fuel oil is produced through a hydrodesulfurization step from a hydrocarbon oil generally obtained as a residual oil obtained from gasoline, kerosene, and light oil (boiling point of about 340 ° C.). There is a demand for less fuel oil.

[0003] Incidentally, in order to simultaneously remove a sulfur compound and a nitrogen compound by treating a hydrocarbon oil, in addition to a conventionally known hydrodesulfurization activity, a hydrodenitrogenation activity for cleaving a C-N bond is required. Is required.

Various studies have been made on catalysts having both hydrodesulfurization and denitrification activities. For example, US Pat. No. 3,446,730 discloses a crystallization water of 1.2 to 2.6. Nickel or a Group 6 metal or an oxide or sulfide of such a metal is supported on an alumina carrier produced by calcining the contained aluminum hydroxide, and 0.1 to 2.6
Catalysts have been proposed to which a promoter consisting of phosphorus, silicon or barium by weight is added, but the properties of the support are not described at all. Moreover, it is described that the treated oil can be applied to any distillate including residual oil, but it is apparent that the distillate is actually applied only to distillate oil.

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

The above-mentioned improvement is disclosed in Japanese Patent Application Laid-Open No. Sho 56-40432.
In the publication, titanium oxide is used as a carrier, and a catalyst in which a group 6 metal and a group 8 metal of the periodic table and phosphorus or boron are similarly supported as a catalyst component is proposed. It is expensive, and it is difficult to increase the specific surface area as compared with alumina due to its physical properties.Moreover, the specific surface area tends to decrease during calcination after supporting the catalyst component, and the pore distribution is desired to be the same as alumina. Difficult to maintain in range.

[0007] As described above, in any of the catalysts, an active metal belonging to Group 6a and Group 8 of the periodic table is supported as a catalyst component together with phosphorus having a catalyst promoting effect, and the acid point of the catalyst. However, for example, even if phosphorus is uniformly supported on the catalyst, there is a disadvantage that if the catalyst is left in the atmosphere, the phosphorus absorbs moisture and the supported state changes.

In general, the method for producing a catalyst for hydrotreating hydrocarbon oils employs a production step in which an inorganic oxide carrier is impregnated with an aqueous active metal solution, dried and then calcined. No attempt has been made to impregnate such a carrier with an aqueous active metal solution and then dry it, and then apply the dried product as it is as a hydrotreating catalyst.

[0009]

DISCLOSURE OF THE INVENTION The present inventors have made improvements in the support for the purpose of increasing the acid point of the support serving as the base of the catalyst. As a result, the support comprising the boria-silica-alumina composition has been obtained. Was found, and the performance of a catalyst in which a conventional metal having a group 6a metal of the periodic table and a metal of the group VIII of the periodic table were carried on the carrier was examined. To satisfy both reactions at the same time, a preferred specific range exists in the composition ratio and pore diameter of the boria-silica-alumina composition as a carrier, and it has been found that a suitable range also exists in the amount of supported metals. Although a patent application was filed with respect to this, the present inventors arrived at the present invention as a result of further intensive studies to improve both hydrodesulfurization and denitrification activities.

That is, the present invention solves the above-mentioned problems of the conventional hydrocarbon oil hydrogenation catalyst, and provides sufficient hydrodesulfurization and denitrification activities of hydrocarbon oil.
Another object of the present invention is to provide a method for producing a catalyst for hydrodesulfurization and denitrification in which the steps are simplified.

[0011]

According to the present invention, in order to achieve the above object, the composition has a range of ₃ to 10% by weight as B ₂ O ₃ and a range of 3 to 8% by weight as SiO ₂ ,
In addition, at least one metal selected from Group 6a metals of the periodic table as an active metal component is used as an active metal component in an oxide carrier of 17 to 28 in terms of oxide on a boria-silica-alumina-based oxide carrier having the following pore characteristics. % By weight and at least one metal selected from Group 8 metals of the periodic table in an amount of from 3 to
A method for producing a catalyst for hydrodesulfurization and denitrification of hydrocarbon oils, comprising impregnating with an aqueous metal salt solution containing 8% by weight and drying.

The oxide carrier based on boria-silica-alumina according to the present invention has a pore characteristic having an average pore diameter of 60 to 90 Å in a pore distribution measured by a mercury intrusion method, and It is necessary that the pore volume in the range of average pore diameter ± 10 angstroms occupy at least 60% of the total pore volume.

As the catalytically active component to be supported, at least one selected from the group 6a metals of the periodic table and at least one selected from the group VIII metals are supported in the above-mentioned content range. It is necessary to impregnate these active metals with an aqueous solution of these active metals and to dry them. The obtained catalyst in a dry state can be subjected to a sulfidation treatment similar to a generally performed method before the hydrogenation treatment, and then used.

[0014]

The details of the present invention and its operation will be described below. Carrier of the present invention, boria - silica - consists alumina composition is in the range that the composition is from 3 to 10% by weight _B 2 _{O 3,} 3 to 8% by weight SiO _2, the balance being _Al 2 _{O 3} Otherwise, no dramatic improvement in denitrification activity is observed. This improvement in activity is considered to be 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 among these, molybdenum is particularly preferred. The metals used as Group 8 metals in the periodic table are iron, cobalt and nickel, and particularly preferred among these are nickel and / or cobalt. Both of the 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, of the Group 6a metal of the periodic table, and 3 to 8% by weight of the Group 8 metal of the periodic table, based on the oxide. It is. And the lower limit of these metal components indicates the minimum necessary for the desired generation of hydrodesulfurization and denitrification activity. No increase is observed.

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

When the average pore diameter of the boria-silica-alumina support is smaller than this, the diffusion resistance of the reactants in the catalyst particles is large, and both hydrodesulfurization and denitrification activities are reduced. Further, even if the average pore diameter of the boria-silica-alumina carrier falls within the range of 60 to 90 Å, when the volume occupied by the average fine pores ± 10 Å is less than 60% of the total pore volume, The pores effective for hydrodesulfurization and denitrification of hydrocarbon oils decrease, and both activities decrease.

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 produced by a general catalyst carrier production method such as a mixing method. A silica hydrate slurry obtained by mixing and hydrolyzing an aqueous solution of aluminum sulfate and sodium aluminate and having a silica content of 3 to 8% by weight as SiO ₂ when used as a catalyst carrier.
An aqueous solution of sodium silicate was added to the mixture, followed by filtration and washing, whereby 0.05 as Na ₂ O was obtained.
A silica-alumina catalyst containing 0.20% by weight as SO ₄ and 0.20% by weight as SO ₄ was obtained, and the boron content was ₃ to 10% by weight as B ₂ O ₃ when the hydrate was used as a carrier. Add an aqueous acid solution, knead until it becomes moldable moisture, cylindrical, spherical, three-leaf type, after molding into a general catalyst support shape such as four-leaf type, dried, then by firing Can be manufactured.

When an organic acid such as gluconic acid or tartaric acid is added during the hydrolysis reaction to obtain the alumina hydrate, it is effective to obtain a catalyst whose pore distribution is concentrated within a specific range. is there.

Further, as a boria raw material used for producing the boria-silica-alumina composition,
For example, boric acid, water-soluble salts such as tetraboric acid, and the like,
Examples of the silica raw material include water-soluble salts such as sodium silicate and silicon tetrachloride. 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.

In order to carry the active metal component on the thus obtained carrier having a desired pore structure of boria-silica-alumina as a base, for example, molybdenum trioxide, nickel carbonate and cobalt carbonate are mixed with water. An organic acid, such as citric acid or tartaric acid, is added to the slurry suspended in water, and an aqueous solution is prepared by heating and dissolving.
The solution is absorbed by impregnating a silica-alumina carrier, and the concentration of the aqueous solution is adjusted so that a desired amount of the active metal component can be supported, or the entire amount of the aqueous solution is absorbed by dissolving the desired active metal. Then, the catalyst of the present invention can be obtained by drying.

In the conventional catalyst production process, a catalyst is obtained by impregnating the carrier with an aqueous solution of an active metal salt, followed by drying and calcining. However, in the production method of the present invention, the catalyst is calcined during the production process. This is advantageous in terms of thermal energy because the step is not required. The catalyst obtained by the production method of the present invention is a catalyst obtained by a conventional catalyst production method of impregnating an oxide carrier with an active metal, drying and calcining in a hydrodesulfurization and denitrification reaction of a hydrocarbon oil. On the other hand, it shows remarkably superior activity as compared with those subjected to the sulfurizing treatment.
Although the reason is not clear, the active metal component contained in the catalyst obtained by final calcination in the prior art is in an oxide state, so that molybdenum sulfide or the like generated in the sulfurization treatment step is used. 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]

Next, an embodiment of the present invention will be described. (1) Manufacture of catalyst carrier Example 1 In a stainless steel reaction tank having an internal volume of 100 liter and equipped with a stirrer, 204 g of a gluconic acid solution (produced by Wako Pure Chemical Industries, Ltd.) with a concentration of 49.5 liters of water (manufactured by Wako Pure Chemical Industries, Ltd.) (0.05% by weight with respect to Al ₂ O ₃ produced by the above) is put into a reaction vessel, heated and maintained at 70 ° C., and stirred with Al ₂ O ₃
Aluminum sulfate aqueous solution containing 774 g
9540 g of Shimada Shoten, 8% sulfuric acid band) and Al ₂
6930 g of an aqueous sodium aluminate 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,
% Of nitric acid to pH 8.3,
O sodium silicate aqueous solution containing 130g as ₂ (manufactured by Wako Pure Chemical Industries (Ltd.)) 929 g by the total amount of added dropwise, pH silica 8.8 - obtain an alumina hydrate. This hydrate was aged for 30 minutes, then 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
A plastic kneaded product having a concentration of 63% by weight as a concentration of ₂ O ₃ —SiO ₂ —Al ₂ O ₃ was obtained.
A boria-silica-alumina carrier containing 5% by weight of B ₂ O _{3 and} 5.7% by weight of SiO ₂ by firing at 700 ° C. for 2 hours in an electric furnace after drying and molding with an extruder having a 5 mmφ die. A was obtained. Example 2 The procedure of Example 1 was repeated, except that the amount of boric acid added to the silica-alumina hydrate obtained in Example 1 was changed, to obtain 3% by weight of B ₂ O _3. , SiO ₂
-Bore-silica-alumina carrier B containing 5.8% by weight as B and 10% by weight as B ₂ O ₃ , and 5% as SiO ₂ .
A boria-silica-alumina support C containing 4% by weight was obtained. Example 3 The amount of the aqueous sodium silicate 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 substantially the same manner as in Example 1 except that O ₂ was changed to 3% by weight and 8.5% by weight, and 2.9% by weight of SiO ₂ and B ₂ O ₃ were respectively added. Boria-silica-alumina support D containing 5% by weight and SiO
_{2 8.1%, B 2 O 3} 5 % by weight of the total composition boria - silica -
An 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 intrusion method, the average pore diameter was in the range of 65 ± 5 angstroms, and the volume occupied by the average pore diameter in the range of ± 10 angstroms was occupied by all the pores. It occupied more than 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.
500 g of the kneaded product was heated and kneaded in a kneader equipped with a heating jacket to obtain a plastic kneaded product having an Al ₂ O ₃ concentration of 60% by weight, and the kneaded product was extruded with a die having a diameter of 1.5 mmφ. And dried in an electric furnace after drying
Calcination was performed at 2 ° C. for 2 hours to obtain an alumina carrier F.

As a result of measuring the pore structure of the obtained carrier F by a mercury intrusion method, the average pore diameter was 70 Å, and the volume occupied by pores having an average pore diameter of ± 10 Å was occupied by all pores. 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 heated and kneaded in a kneader equipped with a heating jacket to obtain a SiO ₂ —Al ₂ O ₃ concentration of 62% by weight of plasticity. Obtain a kneaded product, and then mold this kneaded product with an extruder having a die having a diameter of 1.5 mmφ,
After drying, the mixture was calcined at 700 ° C. for 2 hours in an electric furnace 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 a mercury intrusion method, the average pore diameter was 71 angstroms, and the volume occupied by pores having an average pore diameter of ± 10 angstroms was occupied by all the pores. 63% of the volume. Comparative Example 3 Except that gluconic acid was not added to the reactor, the same procedure as in Example 1 was repeated to obtain 5% by weight of B ₂ O ₃ and Si.
Boria as O ₂ containing 5.7 wt% - Silica - was obtained alumina carrier H.

As a result of measuring the pore structure of the obtained carrier H by a mercury intrusion method, the average pore diameter was 69 Å, and the volume occupied by pores having an average pore diameter of ± 10 Å was occupied by all the pores. 48% of the volume.

Prepared in Examples 1-3 and Comparative Examples 1-3
Pore structure measured by mercury intrusion method
Tables 1 and 2 show the values of(2) Preparation of catalyst  Example 4 Molybdenum trioxide 23.4 g, nickel carbonate 11.8 g
In 50 g of water, add 2.0 g of tartaric acid and heat
And adjust the volume with water to match the volume of water absorbed by the carrier.
The impregnated liquids obtained were obtained in Examples 1, 2 and 3.
Average pore diameter within the range of the present invention, average pore diameter ± 10 mm
The volume occupied by pores in the range of
Having a pore structure such that it is 60% or more of
Rica-alumina carriers A, B, C, D and E each of 100
g, impregnated for 2 hours and dried at 110 ° C for 16 hours
And 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) and
And carrier H (having a pore structure outside the scope of the present invention)
(Except for using boria-silica-alumina carrier)
Catalysts N, O and P were obtained in substantially the same procedure as in Example 4. Example 5 Molybdenum trioxide 39.7 g, nickel carbonate 13.4 g
In 50 g of water, add 2.0 g of tartaric acid and heat
And adjust the volume with water to match the volume of water absorbed by the carrier.
The obtained impregnating solution was obtained using the boria-silica-aluminum obtained in Example 1.
Impregnated in 100 g of carrier A and left at 110 ° C for 2 hours
After drying for 16 hours, catalyst Q was obtained.

Also, 23.4 g of molybdenum trioxide and 16.5 g of nickel carbonate were suspended in 50 g of water, and 2.0 g of tartaric acid was suspended.
And dissolved under heating, and impregnated with 100 g of the boria-silica-alumina carrier A obtained in Example 1 with the impregnating solution whose volume was adjusted with water to a volume corresponding to the water absorption of the carrier, and 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 Molybdenum trioxide 39.7 g, cobalt carbonate 12.2 g
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 as the boria-silica obtained in Example 1. -Impregnated into 100 g of alumina simple substance A, left for 2 hours, dried at 110 ° C for 16 hours, and then calcined at 500 ° C for 2 hours to obtain Catalyst S.

Also, 23.4 g of molybdenum trioxide and 15.1 g of cobalt carbonate were suspended in 50 g of water, and 2.0 g of tartaric acid was suspended.
And dissolved under heating, and impregnated with 100 g of the boria-silica-alumina carrier A obtained in Example 1 with the impregnating solution whose volume was adjusted with water to a volume corresponding to the water absorption of the carrier, and 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 14.0 g of molybdenum trioxide and 4.2 g of nickel carbonate were suspended in 50 g of water, dissolved under heating, and the impregnating liquid was adjusted with water to a liquid amount corresponding to the water absorption of the carrier. 100 g of the boria-silica-alumina carrier A obtained in 1 was impregnated, left for 2 hours, dried at 110 ° C. for 16 hours,
It was calcined at 00 ° C. for 2 hours to obtain a catalyst U.

In the catalyst U, the supported amounts in terms of MoO ₃ and NiO were both smaller 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 impregnation liquid obtained by adjusting the amount of water with water to a liquid amount corresponding to the amount of water absorbed by the carrier was obtained in Example 1. 100 g of each of the silica-alumina carrier A, the alumina carrier F obtained in Comparative Example 1 and the silica-alumina carrier G obtained in Comparative Example 2 were respectively impregnated, left for 2 hours, dried at 110 ° C. for 16 hours, and then 500 Calcination was performed 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 the present invention. (3) Catalyst performance evaluation test The activity of hydrodesulfurization and denitrification of hydrocarbon oil was examined for various catalysts shown in Tables 1 and 2 using a fixed bed flow reactor with a catalyst loading of 15 ml.

The catalyst was sulfurized under a light gas oil containing 2.5% by weight of dimethyl disulfide, a hydrogen / oil supply ratio of 200 Nl / l, and an LHSV of 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 to perform preliminary sulfurization.

Next, a sulfur content of 1.15% by weight and a nitrogen content of 6%
Using quat ordinary pressure light oil containing 8 ppm, pressure 30 kg
/ Cm ² G, LHSV = 2.0 hr ⁻¹ , hydrogen / oil supply ratio 300 Nl / l, temperature 300 ° C., and analyze the sulfur content and nitrogen content in the treated oil 100 hours after the start of the reaction Table 1 shows the desulfurization rate and denitrification rate.
It was shown to.

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

The desulfurization rate and denitrification rate of the catalyst W shown in Table 2 were set to 100 because the catalyst W was prepared by a conventional method for producing a hydrotreating catalyst. This is because it has almost the same characteristics as those commercially available as a catalyst in which MoO ₃ , NiO and P ₂ O ₆ are supported on a carrier having alumina as a base as an active catalyst.

[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 Regarding the composition ratio of the composition, the average pore diameter and the pore distribution, and the amount of active metal supported, the catalyst must satisfy the range specified in the present invention, and exhibit a high desulfurization rate and a high denitrification rate. Is evident.
On the other hand, in the catalyst P, the amount of the active metal carried and the composition ratio of the boria-silica-alumina carrier belong to the range defined in the present invention. ) Value remains at 48% and the pore distribution is broad, so that the desulfurization and denitrification rates of this catalyst P are
This value is lower than that of Catalyst I having a narrower pore distribution.

The catalyst N and the catalyst O belong to the range defined in the present invention with respect to the amount of active metal carried, the average pore diameter 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.

The catalysts Q, R and U in Table 2
Although the composition ratio of boria-silica-alumina support, the average pore diameter and the pore distribution satisfy the scope of the present invention, the amount of molybdenum and nickel in terms of oxide conversion is different from catalyst I. It has changed. That is, the catalyst Q has an increased amount of molybdenum as compared with the catalyst I, and the catalyst R has an increased amount of nickel as compared with the catalyst I.
All are within the scope of the present invention and show sufficiently high desulfurization and denitrification rates. However, catalyst U has a reduced amount of molybdenum and nickel as compared to catalyst I, and since its content is out of 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 composed of 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 is obtained by supporting cobalt instead of nickel as an active metal in an amount within the scope of the present invention. It shows high desulfurization and denitrification rates.

The catalyst V falls within the scope of the present invention with respect to the composition ratio, average pore diameter and pore distribution of the boria-silica-alumina carrier, but 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 when the acid point of the carrier is low to improve the desulfurization and denitrification activity by adding phosphorus as a co-catalyst, but the carrier based on boria-silica-alumina of the present invention is However, since the acid point is basically higher than that of a commonly used alumina-based carrier, when phosphorus is carried, the acid point becomes too high, and the desulfurization rate and the denitrification rate are rather lowered.

The catalyst X is obtained by supporting molybdenum and nickel as active metals on silica-alumina alone. The average pore diameter and the pore distribution fall within the ranges defined in the present invention. Although the desulfurization and denitrification activities are somewhat improved as compared with the catalyst, the values are all lower than that 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 performs desulfurization and denitrification much more efficiently than conventionally proposed catalysts of this kind. be able to. Therefore, if the catalyst of the present invention is used 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 (2)

(57) [Claims] The composition has a composition of ₃ to 10% by weight as B ₂ O ₃ and a content of 3 to 8% by weight as SiO ₂ , and has a pore distribution of a pore distribution measured by a mercury intrusion method. 6
An oxide carrier based on boria-silica-alumina having an average pore diameter of 0 to 90 angstroms and having a pore volume in the range of an average pore diameter ± 10 angstroms of 60% or more of the total pore volume. On the other hand, at least one selected from Group 6a metals of the periodic table as the active metal component
Impregnated with a metal salt aqueous solution containing 17 to 28% by weight of a metal in an oxide equivalent and 3 to 8% by weight of an oxide of at least one metal selected from Group VIII metals of the periodic table. A method for producing a catalyst for hydrodesulfurization and denitrification of hydrocarbon oils, characterized by drying. 2. The active metal component may be a 6a of the periodic table.
2. 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 VIII metal of the periodic table is at least one of nickel and cobalt. .