JP2817558B2 - Catalyst for hydrodesulfurization and denitrification of hydrocarbon oil and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrotreating catalyst for effectively removing both a sulfur compound and a nitrogen compound contained in a hydrocarbon oil, and particularly to a sulfur compound and a nitrogen compound. Desulfurization of hydrocarbon oils that can reduce the sulfur and nitrogen contents in the raw hydrocarbon oils simultaneously by converting hydrocarbon oils containing large amounts of hydrogen into hydrogen sulfide and ammonia by treating them under hydrogen pressure The present invention relates to a denitrification catalyst and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, as a method for removing a sulfur compound and a nitrogen compound contained in a hydrocarbon oil, a method in which a hydrocarbon oil is brought into contact with a catalyst under a high-temperature and high-pressure reaction condition in the presence of hydrogen to perform a hydrotreatment. It has been known. The hydrodesulfurization method is one of the hydrotreating methods, in which a catalyst for hydrotreating is carried out on a porous alumina carrier by using a metal of Group VIa of the periodic table and a metal of Group VIa.
Catalysts supporting Group VIII metals are commonly used.
However, this hydrotreating catalyst shows high activity for hydrodesulfurization reaction but does not show sufficient activity for hydrodenitrogenation reaction. That is, under the commonly used hydrodesulfurization conditions, the hydrodesulfurization activity is extremely low with respect to the hydrodesulfurization activity. Therefore,
In order to sufficiently perform the hydrodenitrogenation reaction using the hydrodesulfurization catalyst, it is necessary to perform the treatment at a high pressure and temperature or at a small space velocity. However, when hydrocarbon oil is actually hydrotreated under such conditions, satisfactory results regarding hydrodenitrogenation can be obtained, but on the other hand, desulfurization or hydrogenation and further lightening are more than necessary. As a result, hydrogen consumption is increased, which is not economically favorable and not practical. Therefore, in order to simultaneously remove sulfur compounds and nitrogen compounds by hydrotreating a hydrocarbon oil, in addition to the conventionally known hydrodesulfurization activity, a hydrodenitrogenation activity that cleaves a C—N bond is required. A catalyst equipped with

Various catalysts having both hydrodesulfurization and denitrification activities have been proposed. For example, U.S. Pat. No. 3,446,930 discloses that an alumina carrier produced by calcining aluminum hydroxide containing water of hydration of 1.2 to 2.6 contains nickel or nickel in the periodic table. VI metal or an oxide or sulfide of the metal,
Catalysts have been proposed in which 1 to 2.0 wt% of a promoter comprising phosphorus, silicon or barium is added. U.S. Pat. No. 3,749,664 describes a catalyst in which molybdenum and nickel or cobalt and phosphorus are supported at a specific ratio on an alumina or silica-alumina carrier. Has a pore volume of 0.6 to 1.4 cc / g. Further, as an improvement described above, JP-A-56-40432 discloses a catalyst in which titanium oxide is used as a carrier, and a catalyst component containing a metal of Group VIa or Group VIII of the periodic table and phosphorus or boron. Has been proposed. Also, Japanese Patent Application Laid-Open No. 4-166,233 proposes a method for producing a catalyst in which an active metal is supported on an inorganic oxide carrier, a polyhydric alcohol or the like is supported on a dried and calcined catalyst, and then dried. I have. The present inventors have focused on increasing the acid point of the carrier serving as the base of the catalyst, and have made improvements and made a specific range of the ratio of polya-silica-alumina, and have a specific range of effective pore diameters, and Polya-silica
It has been found that the activity of hydrodesulfurization and denitrification can be improved by using an active metal supported on an alumina oxide catalyst carrier in a dried state as a catalyst (Japanese Patent Application No. 4-214, proposed). 513).

[0004]

However, U.S. Pat. No. 3,446,730 does not disclose the characteristics of the carrier and further treats the treated oil in any fraction, including residual oil. Is applicable, but it is understood that it is actually intended for distillate oil. Also, US Pat. No. 3,749,664 does not study the pore structure of the carrier and does not have satisfactory performance for hydrotreating hydrocarbon oils. further,
In JP-A-56-40432, titanium oxide used as a carrier is expensive, and its physical properties make it difficult to increase the specific surface area as compared with alumina. Surface area is easy to decrease,
It is difficult to maintain the pore distribution in a desired range like alumina. Japanese Patent Application Laid-Open No. 4-166,233 discloses alumina as an inorganic oxide carrier, but does not describe its characteristics. Further, in this method for producing a catalyst, after carrying an active metal, the catalyst is dried or calcined. Since it supports polyhydric alcohol and the like, the process is complicated, and further, nothing is described about the effect as a hydrodenitrogenation catalyst.

SUMMARY OF THE INVENTION An object of the present invention is to provide a catalyst which has both hydrodesulfurization and denitrification activities of a hydrocarbon oil and which simplifies the catalyst production process, and a method for producing the same. It is.

[0006]

Means for Solving the Problems In order to solve the above problems and to achieve the above object, the present inventors have studied a catalyst in which an active metal is supported on an oxide catalyst carrier composed of poly-silica-alumina. As a result of stacking, on the catalyst support,
After supporting the active metal and the dihydric alcohol, it was found that by using the catalyst in a dry state, both the activities of hydrodesulfurization and denitrification could be improved to achieve the object, and the present invention was completed. . That is, the present invention relates to polya-silica
Catalyst for hydrodesulfurization and denitrification of hydrocarbon oil which is a dried product in which at least one of Group VIa metal and Group VIII metal of the periodic table and an dihydric alcohol are supported as active metals on an oxide catalyst carrier comprising alumina An oxide catalyst carrier comprising polya-silica-alumina is loaded with an impregnating liquid to which at least one of a Group VIa metal and a Group VIII metal of the periodic table and a dihydric alcohol are added as active metal components, This is a method for producing a catalyst for hydrodesulfurization and denitrification of a hydrocarbon oil which has been dried and used as a dried catalyst.

Thus, the catalyst carrier in the present invention is an oxide carrier composed of poly-silica-alumina,
The content of polya and silica is in the range of ₃ to 10% by weight as B ₂ O ₃ and 3 to 8% by weight as SiO ₂ , and the physical properties of the carrier are pores measured by a mercury intrusion method. It is preferable to use those having an average pore diameter of 55 to 85 angstroms in distribution and having a pore volume in the range of an average pore diameter ± 10 angstroms of at least 60% of the total pore volume. Such a carrier having a narrow pore distribution and a desired average pore diameter can be produced by a general method such as a mixing method. That is, an aqueous solution of aluminum sulfate and an aqueous solution of sodium aluminate are mixed and hydrolyzed, and the resulting alumina hydrate slurry has a silica content of 3 as SiO ₂ when used as a carrier.
An aqueous solution of sodium silicate was added so as to be 8% by weight, filtered and washed to obtain 0.05% by weight as Na ₂ O,
A silica-alumina hydrate containing 0.20% by weight as SiO ₂ is obtained, and a boric acid aqueous solution is added to the hydrate so that the polya content when used as a carrier is ₃ to 10% by weight as B ₂ O _3. Is added, kneaded to formable moisture, and after sufficient plasticization, cylindrical, spherical, three-lobe, after molding into a shape as a general catalyst carrier such as four-leaf as required,
It can be manufactured by a method of drying and then firing. In addition, by adding an organic acid such as gluconic acid or tartaric acid at the time of hydrolysis for obtaining the alumina hydrate, it is possible to effectively obtain a catalyst whose pore distribution is concentrated in a specific range. Further, as a raw material of Poria used when producing the carrier, for example, boric acid, water-soluble salts such as tetraboric acid, and the like, as a raw material of silica, for example,
Examples thereof include water-soluble salts such as sodium silicate and silicon tetrachloride. Examples of the alumina raw material include aluminum nitrate, aluminum sulfate, and sodium aluminate, and water-soluble salts thereof.

The group VIa metal of the periodic table used as the hydrogenation active metal component is chromium, molybdenum or tungsten, with molybdenum being particularly preferred. or,
The Group VIII metal is iron, cobalt, nickel, particularly preferably nickel and / or cobalt, and most preferably a combination of these. The loading amount of the active component is from 17 to 28% by weight, based on the total weight of the catalyst, of the Group VIa metal, and from 3 to 8% by weight of the Group VIII metal, based on the oxide. Is preferred.

As the dihydric alcohol, it is preferable to use diethylene glycol or triethylene glycol. The amount of the dihydric alcohol is preferably 0 to the total molar amount of the Group VIa and Group VIII metals supported as the active metal component. A range of 0.2 to 3 times is preferable.

[0010] Further, the drying temperature after supporting the impregnating liquid containing an active metal and a dihydric alcohol on the carrier is preferably 200 ° C or less.

[0011]

The oxide catalyst carrier composed of polya-silica-alumina and the contents of polya and silica in the above range are as follows.
If the composition is not in the above-mentioned range, no remarkable improvement in denitrification activity is recognized, and this improvement is considered to be due to a synergistic effect of the three components in the above-mentioned range of the carrier. Regarding the pore diameter and pore distribution of this carrier,
In order to increase the number of pores having a pore diameter effective for denitrification as much as possible and to suppress other harmful reactions, it is necessary that the pore distribution is narrow and the average pore diameter is a specific value. When the average pore diameter is less than the lower limit,
When the diffusion resistance of the reactants in the catalyst particles is large, the activities of both hydrodesulfurization and dehydrogenation decrease, and when the average pore diameter exceeds the upper limit, a large amount of the reactants penetrate into the pores at once. However, the deposition of carbonaceous matter by the decomposition lowers both hydrodesulfurization and denitrification activities. Further, when the pore distribution is not concentrated in the specific range as described above, even if the average pore diameter is within the range, it is effective for hydrodesulfurization and denitrification of hydrocarbon oil. Since the pores are reduced, both activities are reduced, and if it is within the above range, the effect of desulfurization and denitrification of the finally obtained dried catalyst is the most excellent.

The reason that the amount of the active metal component carried is preferably in the above-mentioned range is that the lower limit of the above-mentioned range is the minimum amount necessary for generating a desired value of hydrodesulfurization / denitrification activity, and the upper limit is: This is because even if the addition amount is further increased, the hydrodesulfurization / denitrification activity is not expected to increase.

The above-mentioned amount of the dihydric alcohol is a necessary amount for forming a complex compound by reacting with the hydrogenation active metal,
If the added amount is less than 0.2 times, a complex compound cannot be sufficiently formed. If the added amount exceeds 3 times, the dihydric alcohol excessively contained in the sulfurization step is not decomposed and converted into carbon as a carbon component in the catalyst. This is because they remain and reduce the hydrodesulfurization / denitrification activity. A similar effect can be obtained even with a polyhydric alcohol having a specific gravity of about 1.1 to 1.2.

[0014] The catalyst of the present invention is prepared by adding a catalyst support made of poly-silica-alumina having a desired pore structure as described above to, for example, molybdenum trioxide and nickel carbonate;
To a slurry in which cobalt carbonate is suspended in water, citric acid, tartaric acid, and other organic acids are added, and diethylene glycol is added to an aqueous solution that has been heated and dissolved, and the entire amount of the impregnating liquid is adsorbed as an amount that can be adsorbed on the carrier, and the entire amount is adsorbed. Then, it can be manufactured by drying at 200 ° C. or lower.

The catalyst prepared by the method of the present invention is obtained by a conventional method for producing a catalyst in which an active metal is supported on an oxide carrier and dried or dried and calcined in a hydrodesulfurization and denitrification reaction of a hydrocarbon oil. It shows superior activity to the catalyst obtained by subjecting the obtained catalyst to a sulfidation treatment. Although the reason cannot be ascertained, the active metal is converted into a sulfide form in the sulfidation step, but it is possible to prevent agglomeration of particles generated at that time, to reduce the particle size of the sulfide, and to form a highly dispersed state. It is thought that it is because it has become.

[0016]

Next, an embodiment of the present invention will be described. Example 1 (1) Preparation of Catalyst Carrier: In a stainless steel reaction tank having an internal volume of 100 liter and equipped with a stirrer, 49.5 liters of water and 204 g of a 50% gluconic acid solution (to Al ₂ O ₃ generated by hydrolysis) were added. 0.05% by weight) in a reaction vessel, heated and maintained at 70 ° C., and stirred while stirring Al _2.
Aluminum sulfate aqueous solution 95 containing 774 g as O ₃
A total of 40 g and an aqueous solution of sodium aluminate containing 1275 g of Al ₂ O ₃ were simultaneously or almost simultaneously added dropwise to obtain an alumina hydrate slurry having a pH of 9.0. Next, the slurry was aged for 30 minutes, and then 25%
g to pH 8.3 and then 13 as SiO _2.
A total of 929 g of an aqueous sodium silicate solution containing 0 g was added dropwise to obtain a silica-alumina hydrate having a pH of 8.8. After aging the hydrate for 30 minutes, the silica-alumina hydrate cake 50 obtained by filtering and washing until Na ₂ O becomes 0.1% by weight or less and SO ₄ becomes 0.5% by weight or less.
00 g (20% by weight as SiO ₂ —Al ₂ O ₃ )
94 g of boric acid (53.2 g as B ₂ O ₃ ) was added, and the mixture was heated and kneaded in a kneader equipped with a heating jacket to obtain B ₂ O ₃ -S
A plastic kneaded product having a concentration of 63% by weight as iO ₂ —Al ₂ O ₃ was obtained.
After being molded by an extrusion molding machine having a die, and dried, the mixture was fired at 700 ° C. for 2 hours in an electric furnace to obtain a catalyst carrier A. The pore structure of the obtained catalyst carrier was measured by a mercury intrusion method. Table 1 shows the measurement results together with the catalyst carrier composition.

(2) Preparation of catalyst: molybdenum trioxide
7 g and 13.4 g of nickel carbonate were suspended in 50 g of water, and 2.0 g of tartaric acid was added and dissolved under heating.
Add 33 g of diethylene glycol, mix well, mix and adjust the amount of impregnating solution with water so that the amount of water matches the amount of water absorbed by the catalyst carrier, and use the catalyst comprising poly-silica-alumina obtained in (1). Impregnate 100 g of carrier A,
After leaving it for 110 hours, it was dried at 110 ° C. for 16 hours to obtain Catalyst 1.

(3) Evaluation of catalyst performance: The obtained catalyst 1 was examined for hydrodesulfurization / denitrification activity of hydrocarbon oil using a fixed bed flow reactor with a catalyst loading of 15 ml.

The catalyst is sulfurized at a hydrogen / oil supply ratio of 200 Nl / l, LHSV = 2.0 hr ^-1 , pressure of 30 with light oil containing 2.5% by weight of dimethyl disulfide.
7 kg / cm ² G from 100 ° C. to 315 ° C.
The temperature was raised over a period of time and maintained, and preliminary sulfurization was performed for 16 hours.

Then, a quat normal pressure gas oil containing 1.15% by weight of sulfur and 68 ppm of nitrogen was used, and the reaction conditions were as follows: pressure 30 kg / cm ² G, LHSV = 2.0 hr
^-1 , hydrogen / oil supply ratio 300 Nl / l, reaction temperature 330
C., and the sulfur content and nitrogen content in the treated oil 50 hours after the start of the reaction were analyzed to determine the desulfurization activity and the denitrification activity. Table 2 shows the results. The analysis of sulfur content
The analysis of nitrogen content was carried out using a model TN-05 manufactured by Mitsubishi Kasei Co., Ltd. using a model SLFA-920 manufactured by HORIBA, Ltd.

The desulfurization activities shown in Table 2 were measured in Comparative Example 5 described later.
The reaction rate constant is a relative activity value when the catalyst W obtained in the above is taken as 100, and the rate order is such that the desulfurization reaction rate is proportional to the 1.75 power of the sulfur concentration of the feedstock oil. Km = LHSV · (1 / n−1) · ｛(1 / S
^n-1 )-(1 / Son ^-1 )}.
Here, n = speed order 1.75, LHSV = space velocity (hr ⁻¹ ), S = sulfur concentration (%) in treated oil, So
= Sulfur concentration (%) in the feedstock. The denitrification activity is indicated by the relative activity value of the reaction rate constant when the catalyst W is 100, and the rate order is such that the denitrification reaction rate is proportional to the 1.0 power of the nitrogen concentration of the feed oil. And Km =
LHSV · 1n (No / N). Here, LHSV = liquid hourly space velocity (hr ^-1 ), No = nitrogen concentration (%) in the treated oil, and N = nitrogen concentration (%) in the feed oil. Example 2 (1) Preparation of catalyst carrier: same as Example 1- (1) except that the amount of boric acid added to the silica-alumina hydrate obtained in Example 1- (1) was changed To prepare a catalyst carrier B,
Table 1 shows the results of determining the pore structure by the mercury intrusion method together with the carrier composition.

(2) Preparation of catalyst: Catalyst 2 was obtained in the same manner as in Example 1- (2) except that the catalyst carrier B obtained in (1) was used.

(3) Performance evaluation of catalyst: Performance evaluation was performed in the same manner as in Example 1- (3), and the results are shown in Table 2. Example 3 (1) Preparation of catalyst carrier: same as Example 1- (1) except that the amount of boric acid added to the silica-alumina hydrate obtained in Example 1- (1) was changed. To prepare a catalyst carrier C,
The pore structure was determined by mercury porosimetry. The results are shown in Table 1 together with the carrier composition.

(2) Preparation of catalyst: Catalyst 3 was obtained in the same manner as in Example 1- (2), except that the catalyst carrier C obtained in (1) was used.

(3) Performance test of catalyst: A performance test was conducted in the same manner as in Example 1- (3), and the results are shown in Table 2. Example 4 (1) Preparation of catalyst support: Example 1 was repeated except that the aqueous solution of sodium silicate added to the alumina hydrate slurry obtained in the same manner as in Example 1- (1) was changed to 3% by weight as SiO _2. 1
-The same treatment as in (1) was performed to prepare a catalyst carrier D, and the pore structure was determined by a mercury intrusion method. The results are shown in Table 1 together with the carrier composition.

(2) Preparation of catalyst: Catalyst 4 was obtained in the same manner as in Example 1- (2), except that the catalyst carrier D obtained in (1) was used.

(3) Performance test of catalyst: A performance test was conducted in the same manner as in Example 1- (3), and the results are shown in Table 2. Example 5 (1) Preparation of catalyst carrier: except for using 8.5 wt% aqueous sodium silicate solution as SiO ₂ to be added in Example 1- (1) an alumina hydrate slurry was obtained in the same manner as, A catalyst carrier E was prepared in the same manner as in Example 1- (1), and the pore structure was determined by a mercury intrusion method. The results are shown in Table 1 together with the carrier composition.

(2) Preparation of catalyst: Catalyst 5 was obtained in the same manner as in Example 1- (2) except that the catalyst carrier E obtained in (1) was used.

(3) Performance test of catalyst: A performance test was conducted in the same manner as in Example 1- (3), and the results are shown in Table 2. Example 6 Using the catalyst carrier A prepared in Example 1- (1), except that 32.0 g of molybdenum trioxide, 18.2 g of nickel carbonate and 30.9 g of ethylene glycol were added. The same treatment as in 2) was carried out to obtain a catalyst 6, and Example 1- (3)
A performance test was performed in the same manner as described above. Table 2 shows the results. Example 7 Example 1- (2) was repeated except that 23.1 g of molybdenum trioxide, 9.3 g of nickel carbonate and 30.9 g of diethylene glycol were added to the catalyst carrier A prepared in Example 1- (1). ) Was obtained in the same manner as in Example 1- (3).
A performance test was performed in the same manner as described above. Table 2 shows the results. Examples 8 and 9 Example 1 except that the amount of diethylene glycol added was 16.5 g (Example 8) and 99.0 g (Example 9).
Catalyst 8 (Example 8) and Catalyst 9 (Example 9) were obtained in the same manner as described above, and a performance test was performed in the same manner as in Example 1- (3). Table 2 shows the results. Example 10 Except that cobalt carbonate was used instead of nickel carbonate,
The same treatment as in Example 1 was performed to obtain a catalyst 10.
A performance test was performed in the same manner as (3). Table 2 shows the results. Example 11 Catalyst 11 was treated in the same manner as in Example 1 except that triethylene glycol was used instead of diethylene glycol.
And a performance test was performed in the same manner as in Example 1- (3).
Table 3 shows the results. Examples 12 to 20 Catalyst 12 (Example 12) was treated in the same manner as in Examples 2 to 10 except that triethylene glycol was used instead of diethylene glycol in Examples 2 to 10.
Catalyst 13 (Example 13), Catalyst 14 (Example 14), Catalyst 15 (Example 15), Catalyst 16 (Example 16), Catalyst 17 (Example 17), Catalyst 18 (Example 18), Catalyst 1
9 (Example 19) and Catalyst 20 (Example 20) were obtained, and a performance test was performed in the same manner as in Example 1- (3). Table 3 shows the results. Comparative Example 1 (1) Preparation of catalyst carrier: 2500 g of alumina hydrate cake obtained by filtering and washing the alumina hydrate slurry obtained in the same manner as in Example 1- (1), kneader equipped with a heating jacket And kneaded in the air, and the Al ₂ O ₃ concentration is 60% by weight.
Then, the kneaded product is molded with an extruder having a die having a diameter of 1.5 mmφ, dried, and calcined at 500 ° C. for 2 hours in an electric furnace to obtain an alumina carrier F. Obtained.

(2) Preparation of catalyst: Catalyst N was obtained in the same manner as in Example 1- (2), except that the alumina carrier F prepared in (1) was used.

(3) Performance test of the catalyst: The obtained catalyst N was subjected to a performance test in the same manner as in Example 1- (3).
Table 2 shows the results. Comparative Example 2 (1) Preparation of Catalyst Carrier: 2500 g of silica-alumina hydrate cake obtained in the same manner as in Example 1- (1) was heated and kneaded in a kneader equipped with a heating jacket to obtain SiO ₂ —Al ₂ O.
₍₃₎ A plastic kneaded material having a concentration of 62% by weight was obtained. Then, the kneaded material was molded by an extruder having a die having a diameter of 1.5 mmφ, dried, and dried at 700 ° C. in an electric furnace at 700 ° C.
Calcination was performed for 6 hours to prepare a silica-alumina support G of 6% by weight as SiO ₂ .

(2) Preparation of catalyst: silica prepared in (1)
A catalyst O was obtained in the same manner as in Example 1- (2) except that the alumina carrier G was used.

(3) Performance test of catalyst: The obtained catalyst O was subjected to a performance test in the same manner as in Example 1- (3).
Table 2 shows the results. Comparative Example 3 (1) Preparation of catalyst carrier: Polya-silica-alumina carrier H was prepared in the same manner as in Example 1- (1), except that gluconic acid was not added into the reactor.

(2) Preparation of catalyst: Boria prepared in (1)
Example 1 was repeated except that the silica-alumina carrier H was used.
The same treatment as in (2) was performed to obtain a catalyst P.

(3) Performance test of catalyst: A performance test was performed on the obtained catalyst P in the same manner as in Example 1- (3).
Table 2 shows the results. Comparative Example 4 18.3 g of molybdenum trioxide, 6.7 g of nickel carbonate,
A catalyst S was obtained in the same manner as in Example 1 except that 18.6 g of diethylene glycol was added, and a performance test of the catalyst was performed in the same manner as in Example 1- (3). Table 2 shows the results. Comparative Example 5 A catalyst W was obtained in the same manner as in Example 1 except that diethylene glycol was not added, and a performance test was performed in the same manner as in Example 1- (3). Table 2 shows the results. Comparative Examples 6 to 9 Comparative Examples 1 to 4 except that triethylene glycol was used instead of diethylene glycol in Comparative Examples 1 to 5.
Catalyst N '(Comparative Example 6), Catalyst O' (Comparative Example 7), Catalyst P '(Comparative Example 8), and Catalyst S' (Comparative Example 9) were obtained in the same manner as in Example 1. A performance test was performed in the same manner. Table 3 shows the results.

[0036]

[Table 1]

[Table 2]

[Table 3]

From these results, the catalysts 1, 2 and
3, 4, 5, 11, 12, 13, 14, and 15 have the same content of molybdenum and nickel in terms of oxide and the same amount of diethylene glycol or triethylene glycol (hereinafter referred to as dihydric alcohol), Regarding the composition ratio of polya-silica-alumina and average pore diameter and pore distribution of the catalyst support and the amount of active metal supported, all satisfy the scope of the present invention, and exhibit high desulfurization and denitrification activity. Is recognized. On the other hand, the catalyst P of the comparative example
And P 'are the amount of the active metal supported and the amount of the dihydric alcohol added, and the composition ratio of polya-silica-alumina of the catalyst support falls within the scope of the present invention, but the average pore diameter of the catalyst support ± the pore volume of angstrom. / The value of the total pore volume (%) is 48%
However, since the pore distribution is wide, the desulfurization and denitrification activities of the catalysts P and P 'are lower than those of the catalyst 1 of the present invention having a narrow pore distribution.

The catalysts N, O, N 'and O' of the comparative examples all fall within the scope of the present invention with respect to the amount of active metal supported, the amount of dihydric alcohol added, the average pore diameter and the pore distribution. However, these catalysts have high desulfurization activity but low denitrification activity because the carrier component does not contain polya and / or silica.

The catalysts 6, 7, 16, and 17 of the examples and the catalysts S and S 'of the comparative examples were prepared by using the polya-silica-alumina composition ratio of the catalyst carrier, the average pore diameter and the pore distribution, The amount satisfies the range of the present invention, but the content of molybdenum and nickel in terms of oxide is changed. Catalysts 6 and 16 are catalysts in which molybdenum is reduced and nickel is increased as compared to catalyst 1,
Catalysts 7 and 17 are catalysts in which molybdenum and nickel are reduced as compared to catalyst 1, but both fall within the scope of the present invention and have sufficiently high desulfurization and denitrification rates. The catalysts S and S ′ of the comparative examples are catalysts in which molybdenum and nickel are reduced as compared with the catalyst 1 of the present invention. However, since the active metal content is out of the range of the present invention, both the desulfurization and denitrification activities are different. It shows a low value.

The catalysts 8, 9, 18 and 19 of the Examples have a polya-silica-alumina composition ratio, average pore diameter and pore distribution, active metal loading and dihydric alcohol loading on the catalyst carrier. In the present invention, the amount of dihydric alcohol supported was changed, but the desulfurization / denitrification activity of this catalyst showed a value equivalent to that of catalyst 1, The amount is 0.2 of the molar amount of the supported active metal.
It is clear that a high activity is exhibited within the range of .about.1.5 times.

The catalysts 10 and 20 of the examples fall within the scope of the present invention with respect to the poly-silica-alumina composition ratio of the carrier, the average pore diameter and the pore distribution, the amount of active metal carried, and the amount of dihydric alcohol carried. But molybdenum as an active metal,
It carries cobalt. It is clear that even when cobalt is supported instead of nickel, both the desulfurization and denitrification activities are high.

The catalyst W of the comparative example falls within the scope of the present invention with respect to the poly-silica-alumina composition ratio of the carrier, the average pore diameter and the pore distribution, and the amount of active metal carried. Is an additive-free catalyst, and the desulfurization / denitrification activity of this catalyst is defined as 100, and the activities of other catalysts are shown as relative values.

[0043]

According to the present invention, since a specific oxide catalyst carrier carries a dihydric alcohol together with an active metal and forms a dried product, the desulfurization / denitrification catalyst is more efficient than conventionally proposed hydrodesulfurization / denitrification catalysts. The denitrification can be performed at the same time, and by using the catalyst of the present invention, a remarkable effect such as a fuel oil having a low sulfur content and a low nitrogen content can be produced.

Claims (6)

(57) [Claims] 1. A dried product in which at least one of a Group VIa metal and a Group VIII metal of the periodic table as an active metal component and a dihydric alcohol are supported as an active metal component on an oxide catalyst carrier comprising poly-silica-alumina. A catalyst for hydrodesulfurization and denitrification of hydrocarbon oils, comprising: 2. The oxide catalyst carrier comprising polya-silica-alumina has a polya and silica content of ₃ to 10% by weight as B ₂ O ₃ and 3 to 8% by weight as SiO ₂ . The physical properties of the catalyst support have an average pore diameter of 55 to 85 Å in a pore distribution measured by a mercury intrusion method, and the pore volume in the range of an average pore diameter of ± 10 Å is a total pore volume. The catalyst for hydrodesulfurization and denitrification of hydrocarbon oil according to claim 1, wherein the catalyst is at least 60% of the volume. 3. The dihydric alcohol supported on the catalyst carrier is diethylene glycol and triethylene glycol, and the supported amount is 0.2 mole of the supported hydrogenation active metal.
The catalyst for hydrodesulfurization and denitrification of a hydrocarbon oil according to claim 1 or 2, wherein the amount is from 3 to 3 times. 4. An impregnating liquid in which at least one of a Group VIa metal and a Group VIII metal of the periodic table and a dihydric alcohol are added as active metal components to an oxide catalyst carrier comprising poly-silica-alumina. A method for producing a catalyst for hydrodesulfurization and denitrification of hydrocarbon oil, wherein the catalyst is subjected to a drying treatment to obtain a dried catalyst. 5. An oxide catalyst carrier comprising polya-silica-alumina, wherein the content of polya and silica is ₃ to 10% by weight as B ₂ O ₃ and 3 to 8% by weight as SiO ₂ , The physical properties of the catalyst support have an average pore diameter of 55 to 85 Å in a pore distribution measured by a mercury intrusion method, and the pore volume in the range of an average pore diameter of ± 10 Å is a total pore volume. The method for producing a catalyst for hydrodesulfurization and denitrification of hydrocarbon oil according to claim 4, wherein the catalyst is at least 60% of the volume. 6. The dihydric alcohol supported on the catalyst carrier is diethylene glycol and triethylene glycol, and the supported amount is 0.2 mole of the supported hydrogenation active metal.
The method for producing a catalyst for hydrodesulfurization and denitrification of a hydrocarbon oil according to claim 4 or 5, wherein the amount is from 3 to 3 times.