JP3106761B2 - 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 sulfur compounds and nitrogen compounds contained in a hydrocarbon oil, there is known a method in which a hydrocarbon oil is brought into contact with a hydrocarbon oil under high-temperature and high-pressure reaction conditions in the presence of hydrogen to carry out hydrotreatment. Have been. The hydrodesulfurization method is one of the hydrotreating methods. As the hydrotreating catalyst, a catalyst in which a group VIa metal and a group VIII metal of the periodic table are supported on a porous alumina carrier is generally used. ing. 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. A catalyst has been proposed which supports a Group VI metal or an oxide or sulfide of such a metal and further contains 0.1 to 2.0% by weight of an accelerator composed of phosphorus, silicon or barium. Also, 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.
In general, the carrier preferably has a pore volume of 0.6 to 1.4 cc / g. Also, JP-A-51-
No. 100,983 proposes an oxide catalyst carrier comprising alumina-boria, on which a metal of Group VIa and Group VIII of the periodic table is supported as a catalyst component.
Also, Japanese Patent Application Laid-Open No. 4-166233 proposes a method for producing a catalyst in which an active metal is supported on an inorganic oxide carrier, and then a polyhydric alcohol or the like is supported on a dried and calcined catalyst and dried. ing.

[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. JP-A-51-100,983 does not sufficiently examine the composition and pore characteristics of the catalyst carrier and does not describe the effect as a hydrodesulfurization catalyst. Also, Japanese Unexamined Patent Publication No. 4-166233 discloses
Although alumina is cited as an inorganic oxide carrier, its properties are not described, and furthermore, in this method for producing a catalyst, after carrying an active metal, drying or calcining, and carrying a polyhydric alcohol or the like, the steps are complicated, Furthermore, nothing is described about the effect as a hydrodenitrogenation catalyst. An object of the present invention is to provide a catalyst having both hydrodesulfurization and denitrification activities of a hydrocarbon oil, and having a simplified catalyst production process, and a method for producing the same.

[0005]

Means for Solving the Problems In order to solve the above problems and achieve the above object, the present inventors have made intensive studies on a catalyst in which an active metal is supported on an oxide catalyst carrier comprising boria-alumina. As a result of the superposition, it has been found that both the activities of hydrodesulfurization and denitrification can be improved and the object can be achieved by forming the catalyst in a dry state after the active metal and the dihydric alcohol are supported on the catalyst carrier. Thus, the present invention has been completed. That is, the catalyst for hydrodesulfurization and denitrification of hydrocarbon oil according to the first embodiment of the present invention has a boron content of ₃ to 15% by weight as B ₂ O ₃ and a physical property of mercury intrusion. 80 to 11 in the pore distribution measured by the method
An active metal catalyst is provided on an oxide catalyst carrier comprising boria-alumina having an average pore diameter of 0 angstrom and having a pore volume in a range of an average pore diameter of ± 10 angstroms of 60% or more of the total pore volume. Characterized in that it is a dried product carrying at least one of a Group VIa metal and a Group VIII metal of the periodic table and a dihydric alcohol as a component, and the dihydric alcohol carried on the catalyst carrier is diethylene glycol or triethylene. Glycol, the amount of which is 0.2 to 3 times the number of moles of the hydrogenation-active metal to be supported, and the method for producing a catalyst for hydrodesulfurization and denitrification of hydrocarbon oil according to the second embodiment. The content of the boria is ₃ to 15% by weight as B ₂ O ₃ , and the physical properties thereof are 80 to 11 based on a pore distribution measured by a mercury intrusion method.
An active metal catalyst is provided on an oxide catalyst carrier comprising boria-alumina having an average pore diameter of 0 angstrom and having a pore volume in a range of an average pore diameter of ± 10 angstroms of 60% or more of the total pore volume. Carrying an impregnating liquid to which at least one of Group VIa metals and Group VIII metals of the periodic table and a dihydric alcohol are added as components, and drying treatment;
Characterized in that the catalyst is in a dry state, and the dihydric alcohol supported on the catalyst carrier is diethylene glycol or triethylene glycol, and the supported amount is 0.2 to 3 times the number of moles of the hydrogenation active metal supported. It is characterized by being.

The catalyst carrier of the present invention is an oxide carrier composed of boria-alumina, and has a boron content of ₃ to 15% by weight as B ₂ O ₃ ,
The physical properties of the carrier were 8 as determined by the mercury intrusion porosimetry.
It is necessary to use one having an average pore diameter of 0 to 110 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. Such a carrier having a narrow pore distribution and an average pore diameter in a specific range 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 is filtered and washed to obtain 0.05% by weight of Na ₂ O, SO ₄
Alumina hydrate containing 0.20% by weight as an aqueous solution of boric acid was added to the hydrate so that the boria content when used as a carrier was ₃ to 15% by weight as B ₂ O ₃ . After kneading to formable moisture, and after sufficient plasticization, cylindrical, spherical, three-leaf, four-leaf, etc., if necessary, molded into a shape as a catalyst carrier, dried and then It can be manufactured by a firing method. 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.
Examples of the boria raw material used in producing the carrier include, for example, water-soluble salts such as boric acid and tetraboric acid. 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 or 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, and the amount added is 0.2 to the total molar amount of the Group VIa metal and Group VIII metal supported in the periodic table as an active metal component. A range of three times is preferred. The drying temperature after supporting the impregnating liquid containing the active metal and the dihydric alcohol on the carrier is preferably 200 ° C. or lower.

[0008]

The reason why the content of boria in the oxide catalyst carrier composed of boria-alumina is set in the above range is that if the composition is out of the above range, no remarkable improvement in denitrification activity is recognized. This is because it is considered to be due to the acid property effect of the carrier. Regarding the pore diameter and pore distribution of this carrier, the pore distribution should be as narrow as possible in order to increase the number of pores having pore diameters effective for desulfurization and denitrification, and to suppress other harmful reactions. When the average pore diameter is required to be a specific value and the average pore diameter is less than the lower limit, the diffusion resistance of the reactant in the catalyst particles is large, and the hydrodesulfurization / desulfurization is performed. When both activities of nitrogen decrease and the average pore diameter exceeds the upper limit, a large amount of the reactant penetrates into the pores at once, and the carbonaceous precipitate due to its decomposition causes both hydrodesulfurization and denitrification. This is because the activity is reduced. 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. Both activities are reduced because the pores are reduced,
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 why the above-mentioned range is preferable for the amount of the active metal component to be loaded 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 addition amount of the dihydric alcohol is a necessary amount for forming a complex compound by reacting with the hydrogenation active metal, and if the addition amount is less than 0.2 times, the complex compound cannot be sufficiently formed. This is because if added in excess of twice the amount, the dihydric alcohol excessively contained in the sulfurization step will not be decomposed and will remain in the catalyst as carbon 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.

[0010] The catalyst of the present invention is formed on a catalyst carrier composed of boria-alumina having a desired pore structure as described above, for example, a slurry in which molybdenum trioxide, nickel carbonate and cobalt carbonate are suspended in water. Diethylene glycol is added to an aqueous solution prepared by adding an organic acid such as citric acid or tartaric acid and dissolved by heating, and the entire amount of the solution is adsorbed so that the entire amount of the solution can be adsorbed on the carrier. can do. The catalyst prepared by the method of the present invention is a catalyst obtained by a conventional catalyst production method 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. Shows an activity superior to that of a catalyst which has been subjected to a sulfidation treatment. Although the reason is not certain, the active metal changes to the sulfide form in the sulfidation step, but the aggregation of the particles generated at that time can be prevented, the particle size of the sulfide is small, and the sulfide is in a highly dispersed state. It is thought that it is because it has become.

[0011]

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.
Aluminum sulfate aqueous solution containing 774 g as ₂ O ₃ 9
An aqueous solution of sodium aluminate containing 540 g and 1275 g of Al ₂ O ₃ was simultaneously or almost simultaneously dripped in the range of pH 8.5 to 9.0 to obtain a pH 8.8 alumina hydrate slurry. Next, after aging this slurry for 30 minutes, 5000 g of alumina hydrate cake obtained by filtering and washing until 0.1% by weight or less as Na ₂ O and 0.5% by weight or less as SO ₄ ( ₂ as Al ₂ O ₃
0% by weight), 197 g of boric acid (111 as B ₂ O ₃ )
The g) was added, and kneaded heated warming a jacketed _{kneader, B 2 O 3 -Al 2 O} 3 concentration to obtain a 63% by weight of a thermoplastic having certain kneaded product as then, diameter 1 The kneaded product .5
Molded with an extrusion molding machine having a mmφ die, dried,
It was calcined at 800 ° 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 3
9.7 g and 13.4 g of nickel carbonate are suspended in 50 g of water, and 2.0 g of tartaric acid is added and dissolved under heating. After cooling, 33 g of diethylene glycol is added, and the mixture is sufficiently stirred and mixed. The impregnating solution, the amount of which was adjusted with water so as to be a liquid amount corresponding to the amount, was impregnated into 100 g of the catalyst support A made of boria-alumina obtained in (1), and
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 reaction activity of hydrocarbon oil using a fixed bed flow reactor with a catalyst loading of 15 ml. The catalyst was sulfurized at a hydrogen / oil supply ratio of 200 Nl / l and LH with light oil to which 2.5% by weight of dimethyl disulfide was added.
The temperature was raised from 100 ° C. to 315 ° C. over 7 hours under the conditions of SV = 2.0 hr ⁻¹ and a pressure of 30 kg / cm ² G, and the pre-sulfurization was performed for 16 hours while maintaining the temperature. 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, L
HSV = 2.0 hr ⁻¹ , hydrogen / oil supply ratio 300 Nl /
1, the reaction temperature was 350 ° 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 the sulfur content was performed using SLFA-920 manufactured by Horiba, Ltd.
Using a mold, the analysis of the nitrogen content was performed using TN-0 manufactured by Mitsubishi Kasei Corporation.
This was performed using a type 5 mold.

The desulfurization activity shown in Table 2 was measured in Comparative Example 8 described later.
The reaction rate constant was expressed as a relative activity value when the catalyst T obtained in the above was taken as 100, and the rate order was such that the desulfurization reaction rate was proportional to the 1.75 power of the sulfur concentration of the feedstock oil. Km = LHSV · (1 / n−1) · ｛(1 / S ⁿ⁻¹ ) −
(1 / So ^n-1 )｝. Where n = speed order 1.75,
LHSV = space velocity (hr ⁻¹ ), S = sulfur concentration (%) in the treated oil, and So = sulfur concentration (%) in the feed oil. 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. Km = LHSV · 1n (No / N). Here, LHSV = liquid space velocity (h
r ^-1 ), No = nitrogen concentration (%) in the treated oil, N = nitrogen concentration (%) in the feed oil.

Example 2 (1) Preparation of catalyst carrier: Example 1- (1) was prepared in the same manner as in Example 1- (1) except that the amount of boric acid added to the alumina hydrate obtained in Example 1- (1) was changed. In the same manner, catalyst carrier B was prepared, and 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 2 was obtained in the same manner as in Example 1- (2), except that 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: Example 1- (1) was repeated except that the amount of boric acid added to the alumina hydrate obtained in Example 1- (1) was changed. Similarly, catalyst carrier C was prepared, 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 3 was obtained in the same manner as in Example 1- (2), except that catalyst carrier C obtained in (1) was used. (3) Performance test of catalyst: A performance test was performed in the same manner as in Example 1- (3), and the results are shown in Table 2. Example 4 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 catalyst 4 was obtained by treating in the same manner as in 2).
A performance test was performed in the same manner as in (3). Table 2 shows the results.

Example 5 Example 1 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). -A catalyst 5 was obtained by treating in the same manner as in (2).
A performance test was performed in the same manner as in (3). Table 2 shows the results. Examples 6 and 7 Example 1 was repeated except that the amount of diethylene glycol added was 16.5 g (Example 6) and 99.0 g (Example 7).
Catalyst 6 (Example 6) and Catalyst 7 (Example 7) 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 8 Except that cobalt carbonate was used instead of nickel carbonate,
The catalyst 8 was obtained by treating in the same manner as in Example 1.
A performance test was performed in the same manner as in (3). Table 2 shows the results.

Example 9 A catalyst 9 was obtained by treating in the same manner as in Example 1 except that triethylene glycol was used instead of diethylene glycol, and a performance test was conducted in the same manner as in Example 1- (3).
Table 3 shows the results. Examples 10 to 16 Catalysts 10 (Example 10) and 11 (Examples) were treated in the same manner as in Examples 2 to 8 except that triethylene glycol was used instead of diethylene glycol in Examples 2 to 8. 11), catalyst 12 (Example 12), catalyst 1
3 (Example 13), catalyst 14 (Example 14), catalyst 15
(Example 15) and a catalyst 16 (Example 16) 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) was heated. The mixture was heated and kneaded in a jacketed kneader to obtain a plastic kneaded product having an Al ₂ O ₃ concentration of 60% by weight, and then the kneaded product was molded using an extruder having a die having a diameter of 1.5 mmφ. ,
After drying, it was calcined at 500 ° C. for 2 hours in an electric furnace to obtain an alumina carrier D. (2) Preparation of catalyst: A catalyst M was obtained in the same manner as in Example 1- (2), except that the alumina carrier D prepared in (1) was used. (3) Performance test of catalyst: The obtained catalyst M 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: A boria-alumina carrier E was prepared in the same manner as in Example 1- (1) except that gluconic acid was not added into the reaction vessel. (2) Preparation of catalyst: Catalyst N was obtained by treating in the same manner as in Example 1- (2) except that boria-alumina carrier E prepared in (1) was used. (3) Performance test of 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 3 (1) Preparation of Catalyst Carrier: The kneaded boria-alumina obtained in Example 1- (1) was molded, dried and calcined in an electric furnace at 500 ° C. for 2 hours. A catalyst carrier F was prepared in the same manner as in Example 1- (1), and 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 O was obtained in the same manner as in Example 1- (2), except that catalyst carrier F 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. Comparative Example 4 (1) Preparation of Catalyst Carrier: Example 1 was repeated except that the boria-alumina kneaded product obtained in Example 1- (1) was molded, dried and calcined in an electric furnace at 900 ° C. for 2 hours. A catalyst carrier G was prepared in the same manner as in (1), and the pore structure was determined by mercury porosimetry. The results are shown in Table 1 together with the carrier composition. (2) Preparation of catalyst: A catalyst P was obtained in the same manner as in Example 1- (2), except that the catalyst carrier G 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.

Comparative Example 5 (1) Preparation of catalyst carrier: Example 1- (1) was prepared in the same manner as in Example 1- (1) except that the amount of boric acid added to the alumina hydrate obtained in Example 1- (1) was changed. Similarly, catalyst carrier H was prepared, and 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 Q was obtained by treating in the same manner as in Example 1- (2) except that catalyst carrier H 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. Comparative Example 6 (1) Preparation of Catalyst Carrier: Same as Example 1- (1) except that the amount of boric acid added to the alumina hydrate obtained in Example 1- (1) was changed. Table 1 shows the results of preparing the catalyst carrier I and determining the pore structure by the mercury intrusion method together with the carrier composition. (2) Preparation of catalyst: Catalyst R was obtained by treating in the same manner as in Example 1- (2) except that catalyst carrier I 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. Comparative Example 7 Molybdenum trioxide 18.3 g, nickel carbonate 6.7 g,
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 8 A catalyst T 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 9 to 15 Comparative Examples 1 to 8 except that triethylene glycol was used instead of diethylene glycol in Comparative Examples 1 to 7.
Catalyst M '(Comparative Example 9), Catalyst N' (Comparative Example 10), Catalyst O '(Comparative Example 11), Catalyst P' (Comparative Example 1)
2), catalyst Q '(Comparative Example 13), catalyst R' (Comparative Example 1)
4), a catalyst S '(Comparative Example 15) was obtained, and Example 1- (3) was obtained.
A performance test was performed in the same manner as described above. Table 3 shows the results.

[0022]

[Table 1]

[0023]

[Table 2]

[0024]

[Table 3]

From these results, the catalysts 1, 2 and
3, 9, 10, and 11 are molybdenum converted to oxides,
The nickel content and the amount of diethylene glycol or triethylene glycol (hereinafter referred to as dihydric alcohol) are the same, and the composition ratio of boria-alumina and the average pore diameter and pore distribution of the catalyst carrier and the amount of active metal carried are , All satisfy the scope of the present invention, and show high desulfurization / denitrification activity. On the other hand, the catalysts N and N 'of Comparative Examples have the amount of active metal carried, the amount of dihydric alcohol added, and the composition ratio of boria-alumina of the catalyst carrier within the scope of the present invention, but the average fineness of the catalyst carrier is small. Since the value of the pore volume of the pore diameter ± 10 angstroms / the total pore volume (%) is only 45% and the pore distribution is wide, the desulfurization / denitrification activity of the catalysts N and N 'is determined by It shows a lower value than Catalyst 1 of the narrow inventive example. The catalysts O, O 'and P, P' of the comparative examples have the amount of the active metal supported, the amount of the dihydric alcohol added, and the composition ratio of boria-alumina of the catalyst carrier within the scope of the present invention. Mean pore diameter values of 73 Å and 115
Angstroms and out of the range of the present invention, the desulfurization / denitrification activity shows a lower value than the catalyst 1 of the present invention. The catalysts M and M 'of the comparative examples all fall within the scope of the present invention with respect to the amount of active metal supported and the amount of dihydric alcohol added, the average pore diameter and the pore distribution. Since they are not contained, the desulfurization activity of these catalysts is high, but the denitrification activity is low.

The catalysts 4, 5, 12, and 13 of the examples and the catalysts S and S 'of the comparative examples were obtained with respect to the composition ratio of boria-alumina, the average pore diameter and the pore distribution of the catalyst carrier, and the amount of the dihydric alcohol added. Satisfies the range of the present invention, but changes the contents of molybdenum and nickel in terms of oxide. Catalysts 4 and 12 are catalysts in which molybdenum is reduced and nickel is increased as compared with catalyst 1, and catalysts 5 and 12 are used.
Reference numeral 13 denotes a catalyst in which molybdenum and nickel are reduced as compared with the catalyst 1, but both are within the scope of the present invention and have a sufficiently high desulfurization and denitrification ratio. Comparative example catalyst S,
S 'is a catalyst in which molybdenum and nickel are reduced as compared with catalyst 1 of the present invention, but since the active metal content is outside the range of the present invention, both the desulfurization and denitrification activities show low values. .

The catalysts 6, 7, 14, and 15 of the examples were prepared according to the following formulas with respect to the composition ratio of boria-alumina, the average pore diameter and the pore distribution, the amount of active metal supported, and the amount of dihydric alcohol supported on the catalyst carrier. The catalysts fall within the scope of the invention, in which the amount of dihydric alcohol supported is changed. The desulfurization and denitrification activity of this catalyst shows a value equivalent to that of catalyst 1, and the amount of dihydric alcohol supported Is 0.2 to 1.
It is clear that high activity is exhibited within the range of 5 times the amount. On the other hand, the catalysts Q, Q 'and R,
R ′ is average pore diameter and pore distribution, active metal loading,
The loading amount of the dihydric alcohol falls within the range of the present invention, but the value of the boron-alumina composition ratio is 1% by weight and 20% by weight as B ₂ O ₃ , which is out of the range of the present invention. The activity shows a lower value than the catalyst 1 of the present invention.

The catalysts 8 and 16 of the examples fall within the scope of the present invention with respect to the composition ratio of boria-alumina, the average pore diameter and the pore distribution, the amount of active metal carried and the amount of dihydric alcohol carried on the catalyst carrier. And molybdenum and cobalt as active metals. It is clear that the desulfurization and denitrification activities are high even if cobalt is supported instead of nickel. The catalyst T of the comparative example is within the scope of the present invention with respect to the carrier-to-alumina composition ratio, the average pore diameter and the pore distribution, and the amount of active metal carried. Where the desulfurization / denitrification activity of this catalyst is taken as 100 and the activities of other catalysts are shown as relative values.

[0029]

As described above, according to the present invention, a specific oxide catalyst carrier carries a dihydric alcohol together with an active metal, and is dried without firing. It is capable of simultaneously performing desulfurization and denitrification more efficiently than a desulfurization / denitrification catalyst. By using the catalyst of the present invention, it is possible to produce a fuel oil having a low sulfur content and a low nitrogen content. A remarkable effect is observed.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-58-112049 (JP, A) JP-A-54-96489 (JP, A) JP-A-4-166232 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) B01J 21/00-38/76

Claims (4)

(57) [Claims] The content of boria is _{3 to 1} as B ₂ O _3.
5% by weight, the physical properties of which are an average pore diameter of 80 to 110 angstroms in a pore distribution measured by a mercury intrusion method, and a pore volume in the range of an average pore diameter of ± 10 angstroms. Drying in which at least one of a Group VIa metal and a Group VIII metal of the periodic table and a dihydric alcohol are supported as active metal components on an oxide catalyst carrier composed of boria-alumina having a total pore volume of 60% or more. A catalyst for hydrodesulfurization and denitrification of hydrocarbon oils, which is a product. 2. The dihydric alcohol to be supported on the catalyst carrier is diethylene glycol or triethylene glycol, and the amount of the supported dihydric alcohol is 0.2% of the number of moles of the hydrogenation-active metal supported.
2. The catalyst for hydrodesulfurization and denitrification of hydrocarbon oil according to claim 1, wherein the amount is from 3 to 3 times. 3. The content of boria is _{3 to 1} as B ₂ O _3.
5% by weight, the physical properties of which are an average pore diameter of 80 to 110 angstroms in a pore distribution measured by a mercury intrusion method, and a pore volume in the range of an average pore diameter of ± 10 angstroms. Impregnation by adding at least one of Group VIa and Group VIII metals and a dihydric alcohol as an active metal component to an oxide catalyst carrier comprising boria-alumina having a total pore volume of 60% or more. A method for producing a catalyst for hydrodesulfurization and denitrification of hydrocarbon oils, comprising supporting a liquid, performing a drying treatment, and forming a dried catalyst. 4. The dihydric alcohol supported on the catalyst carrier is diethylene glycol or triethylene glycol, and the supported amount is 0.2 mole of the supported hydrogenation active metal.
4. The method for producing a catalyst for hydrodesulfurization and denitrification of hydrocarbon oil according to claim 3, wherein the amount is from 3 to 3 times.