JPH081009A - Catalyst for hydrogenation of hydrocarbon oil and its production - Google Patents

Abstract

PURPOSE:To simplify the activation process of the catalyst by adding a soln. of hydrogenation active metal belonging to VI group metals and VIII group metals, phosphoric acid, polyhydric alcohol and org. sulfur compd. to an alumina hydrate having a pseudo-boehmite structure, kneading, molding and drying at specified temp. CONSTITUTION:To alumina hydrate having pseudo-boehmite structure, VI group metal by 15-30wt.% oxide and VIII group metal by 3-8wt.% expressed in terms of oxide as hydrogenating active metal and phosphoric acid by 2-8wt.% expressed in terms of oxide are added to obtain the source material of the catalyst. Further, specified amts. of polyhydric alcohol and org. sulfur compd. soln. are added as additives. The mixture is kneaded, molded, and then dried at <=150 deg.C. Thereby, desulfurization and denitrification by hydrogenation can be extremely efficiently performed.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art In recent years, when exhaust gas such as fuel has been called for environmental destruction, there is an increasing demand for reduction of sulfur and nitrogen contained in heavy oil, light oil and the like.

Conventionally, in a so-called hydrotreating step in which hydrocarbon oil obtained from crude oil or coal is subjected to desulfurization, denitrification, decomposition and the like in the presence of hydrogen, hydrogen is applied to a carrier of an inorganic oxide such as γ-alumina. As the activating metal, a catalyst supporting molybdenum and tungsten of Group 6 of the periodic table and cobalt and nickel of Group 8 is used. It is also known that a catalyst using cobalt and molybdenum as hydrogenation-active metals has a high hydrodesulfurization activity, and a catalyst using nickel and molybdenum has a high hydrodenitrogenation activity.

[0004] For these catalysts, for example, alumina hydrate having a pseudo-boehmite structure is molded and then calcined at a temperature of 400 ° C or higher to obtain a γ-alumina carrier, on which molybdenum, tungsten, cobalt, nickel, etc. are formed. Impregnated with the active metal salt aqueous solution described above and dried at about 100 ° C.
It is obtained by firing at about 00 to 600 ° C.

The hydrotreating catalyst thus obtained has no active as it is because the active metal is supported in the form of an oxide, and therefore cannot be used as a catalyst.
Therefore, at the time of use, in order to develop hydrogenation activity, the above catalyst is charged into a reaction tower, and then oil and hydrogen in which a sulfidizing agent is added to light oil or the like is fed into the reaction tower to remove each active metal of the catalyst. A so-called pre-sulfurization treatment is carried out to change from an oxide form to a sulfide form, and then hydrocarbon oil and hydrogen are fed in to start the operation.

However, the conventional catalysts cannot always sufficiently meet the strict requirements for reducing the sulfur content and the nitrogen content,
Although various studies have already been attempted, a catalyst having a sufficiently satisfactory performance has not yet been provided.

In the hydrotreating catalyst, the active sites of the catalyst are formed on the surface of the active metal sulfide, and the larger the external surface area of the active metal sulfide, the greater the number of active sites and the more highly active the catalyst is. It is known to be obtained.

The applicant of the present invention has previously filed Japanese Patent Application Laid-Open No. 4-243535.
No. 47, the active material of molybdenum or tungsten, cobalt or nickel, phosphorus, and 0.3 to 3 of the total number of active metal moles are contained in a carrier material containing one or both of an inorganic oxide and a hydrate thereof as main components. .5 times the amount of one kind of carboxylic acid such as glycolic acid or tartaric acid, and 0.1 times or more the amount of mercaptoacetic acid or thiodiglycolic acid necessary for converting the active metal into the sulfide form. , A kind of organic sulfur compound such as β-thiodiglycol, kneading, molding, and then drying at a temperature of 200 ° C. or lower are disclosed. This catalyst manufacturing method is
It was characterized by the fact that it was not calcined and that the active metal was supported in the sulfide state, so that it could be used as it was without pre-sulfurization treatment, achieving high dispersion of the active metal sulfide. . However, no mention is made of physical properties such as the pore structure of the catalyst. Therefore, even if high activity per weight of catalyst is obtained,
There is a problem that the activity per volume of the catalyst does not increase. It should be noted that JP-A-4-243547 only mentions hydrodesulfurization performance, and does not specifically describe denitrification performance.

[0009]

DISCLOSURE OF THE INVENTION The present invention solves the problems of the conventional catalysts as described above, is sufficiently equipped with both hydrodesulfurization and denitrification activities of hydrocarbon oil, and It is intended to provide a catalyst in which the activation process is simplified.

[0010]

As a result of various studies to solve the above problems, the present inventors have found that the oxide conversion amount of alumina hydrate having a pseudo-boehmite structure is compared with that of Group 6 of the periodic table. An aqueous hydrogenation-active metal solution having an oxide equivalent of molybdenum of 15 to 30% by weight and an oxide equivalent of nickel and / or cobalt of Group 8 metal of the periodic table of 3 to 8% by weight, 2-8% by weight of phosphoric acid converted to oxide
In the hydrodesulfurization / denitrification catalyst raw material having and, the addition amount of the polyhydric alcohol of diethylene glycol and / or triethylene glycol is determined by the Group 6 metal and the 8th group of the periodic table.
The amount of β-thiodiglycol, which is an organic sulfur compound, is 0.1 to 1 times the total molar amount of the group metals so that the Group 6 metal and the Group 8 metal of the Periodic Table are in the sulfide form. In an amount of 0.1 times or more the amount necessary for the above, kneading, molding, and then drying at a temperature of 150 ° C. or lower to obtain a dried catalyst, and the dried catalyst was calcined at 500 ° C. . As a result, the total pore volume measured by the nitrogen adsorption method was 0.6 ml / g.
A hydrotreating catalyst having an average pore diameter of 80 to 100 Å and a pore volume in the range of average pore diameter ± 10 Å of 60% or more of the total pore volume, The inventors have found that this catalyst can provide a hydrodesulfurization / denitrogenation catalyst having higher activity than conventional hydrocarbon oils, and have completed the present invention.

[0011]

In the structure of the catalyst according to the present invention, molybdenum, which is a metal of Group 6 of the periodic table, is 15 to 30% by weight in terms of oxide with respect to hydrated alumina as a hydrogenation active metal,
Nickel and / or cobalt of Group 8 metal of the Periodic Table is 3 to 8% by weight in terms of oxide, and phosphoric acid is added in an amount of 2 to 8% in terms of oxide to obtain a highly active catalyst. Obtaining follows known techniques.

In the method of the present invention, a solution of a hydrated alumina hydrate having a pseudo-boehmite structure containing a predetermined amount of a hydrogenation-active metal and phosphorus as described above is further added with a predetermined amount of a polyhydric alcohol and a predetermined amount as additives. After adding the organic sulfur compound solution in (1), the mixture was kneaded, molded, and then dried at a temperature of 150 ° C. or lower. The dried catalyst was calcined at 500 ° C., and the pore structure of the calcined product was measured by a nitrogen adsorption method. As a result, the total pore volume was 0.6 ml / g or less, and the average pore diameter was 80 to
100 angstrom and average pore diameter ± 1
The pore volume in the range of 0 Å is 6 of the total pore volume.
It was found that the effect of hydrodesulfurization / denitrification of the dry catalyst was the best as a catalyst when it was 0% or more.

When the average pore diameter after calcination of the dry catalyst at 500 ° C. is less than 80 Å,
Nitrogen compounds in hydrocarbon oils have a larger molecular size than sulfur compounds and have higher diffusion resistance in the catalyst particles, so the denitrification activity decreases, while when the average pore diameter is greater than 100 angstroms, the reactants Since a large amount of these enter into the pores and react with each other, carbonaceous matter is ejected to reduce both hydrodesulfurization and denitrification activities. Further, when the pore volume in the range of average pore diameter ± 10 angstrom is 60% or less of the total pore volume, that is, when the pore distribution is not concentrated in a specific range, even if the average pore diameter is 80 to Even if it is in the range of 100 angstroms, both activities are reduced because the number of pores effective for hydrodesulfurization and denitrification of hydrocarbon oil is reduced. Further, the reason why the total pore volume determined by the nitrogen adsorption method is 0.6 ml / g or less is to enhance the activity per volume of the catalyst.

A method for producing an alumina hydrate having a pseudo-boehmite structure used in the present invention is described in JP-A-55-
It can be obtained by the production method described in Japanese Patent No. 27830 and JP-A No. 62-226811. For example, an alumina hydrate slurry produced by hydrolysis by simultaneously dropping an aqueous solution of aluminum sulfate and an aqueous solution of sodium aluminate is used. It can also be obtained by filtration and washing.

Next, phosphoric acid was added to a slurry prepared by suspending molybdenum trioxide and nickel carbonate and / or cobalt carbonate in the above-mentioned alumina hydrate, and the mixture was heated and dissolved.
After adding a solution containing polyhydric alcohol and an organic sulfur compound solution, kneading to a moldable water content, and sufficiently plasticizing, a general desired catalyst such as a cylindrical type, a three-leaf type, a four-leaf type, or a spherical type. After forming into a shape, it is dried. Thereby, the hydrotreating catalyst of the present invention can be manufactured.

The polyhydric alcohol used in the present invention includes
Aliphatic alcohols, preferably diethylene glycol and triethylene glycol, are added in an amount of 0.1 to 1 times the total molar amount of metals of molybdenum, nickel and / or cobalt for hydrodesulfurization and denitrification activity. It was obtained from the necessary amount for the effect to appear. If it is less than 0.1 times, a sufficient effect cannot be obtained, and even if it is added 1 time or more, a large effect for improving the activity can be obtained even if the addition amount is increased. Because I can't.

The organic sulfur compound used in the present invention is β-thiodiglycol, and its addition amount is 0.1, which is an amount necessary for converting the Group 6 metal and the Group 8 metal of the periodic table into the sulfide form.
The amount is double or more, and the amount of 0.1 to 0.5 is sufficient. Even if added more than this, the catalytic activity will not be significantly improved, and considering the manufacturing cost, the addition amount of the organic sulfur compound should be small. Further, as the organic sulfur compound, there are mercaptoacetic acid, thioacetic acid and the like, but it is better to avoid applying them because they contain acetic acid and there is a strong possibility of corroding the reaction tower.

As the drying temperature of the catalyst of the present invention, a temperature at which the added polyhydric alcohol and the organic sulfur compound are not exerted or decomposed may be selected, but the catalyst may be dried at a temperature of 150 ° C. or lower. desirable. The dried catalyst thus obtained is directly charged into a reaction tower, and while being heated and pressurized while feeding light oil and hydrogen gas, it is put into practical use.

It is not clear why the activity of the catalyst of the present invention is significantly improved. With the above-mentioned hydroxycarboxylic acid, formation of an active metal complex ion is considered, but the coordination ability of the polyhydric alcohol used in the present invention is weak,
It cannot be considered the main cause. Rather, in a solution containing active metal, phosphorus, and polyhydric alcohol, the polyhydric alcohol weakens the adsorption rate of alumina and phosphorus, which has a strong adsorptive power, and the active metal and phosphorus are uniformly dispersed and adsorbed on the alumina particles. By immobilizing and suppressing active metal quasi-assembly, and by adding an organic sulfur compound, sulfurization of the active metal was promoted and became uniform, the surface area of the active metal sulfide was increased, and high activity was exhibited. It is considered to be something. Furthermore, it is considered that the activity per volume of the catalyst was increased by limiting the physical properties of the catalyst, that is, the pore structure.

[0020]

EXAMPLES Specific examples and comparative examples of the present invention will be shown below.

(Example 1) 49.5 liters of water and a gluconic acid solution having a concentration of 50% (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a stainless steel reactor equipped with a stirrer and having an internal volume of 100 liters.
08g (0.05 against Al ₂ O ₃ produced by hydrolysis)
Put wt%) and was kept warm to 70 ° C., stirring, Al ₂ O ₃ as a 8.1 wt% containing aqueous aluminum sulfate solution (Co. Shimada Shoten sale, aluminum sulfate) 9540G and Al ₂ O ₃ Aqueous solution of sodium aluminate containing 18.4% by weight (NA-170 manufactured by Sumitomo Chemical Co., Ltd.) 6930
The whole amount was mixed with g to obtain a slurry of alumina hydrate having a pH of 8.8.

Next, the slurry was aged while stirring for 30 minutes, filtered and washed to obtain an alumina hydrate cake.

Next, in a kneader with a heating jacket, 2000 g of the alumina hydrate cake (5% as Al ₂ O ₃₎ was added.
00g), 122 g of molybdenum trioxide, 49 g of nickel carbonate, 44 g of 85% phosphoric acid, and water are dissolved by heating, 54 g of diethylene glycol and 86 g of β-thiodiglycol are added to this, and the mixture is heated at 70 ° C. After kneading and sufficiently plasticizing, the mixture was molded by an extrusion molding machine equipped with a die having a diameter of 1.7 mm and dried at 100 ° C. for 15 hours to obtain a catalyst A.

The metal content of catalyst A is 1 as MoO _3.
8% by weight, 4% by weight as NiO and 4% by weight as P ₂ O ₅ , the addition amount of diethylene glycol was 0.25 times the metal mole number of molybdenum and nickel, and the addition amount of β-thiodiglycol was Molybdenum and nickel were 0.3 times the amounts required to form MoS ₂ and NiS, respectively.

The total pore volume measured by the nitrogen adsorption method after part of the catalyst A was calcined at 500 ° C. for 2 hours was 0.49.
ml / g, the average pore diameter was 82 Å, and the pore volume in the range of the average pore diameter ± 10 Å was 61% of the total pore volume.

The activity was evaluated by using a fixed bed flow reactor with a catalyst loading of 15 ml, and adding hydrogen and light oil to a hydrogen / oil supply ratio of 2
00 Nl / l, liquid hourly space velocity 2.0 hr ^-1 , pressure 30 kg
The temperature was raised from 100 ° C to 315 ° C over 7 hours under the condition of 1 / cm ² G, and then the sulfur content was 1.15% by weight and the nitrogen content was 68.
Using quat atmospheric gas oil containing ppm by weight, pressure 30k
The reaction was carried out under the reaction conditions of g / cm ² G, liquid hourly space velocity of 2.0 hr ⁻¹ , hydrogen / oil supply ratio of 200 Nl / l, and temperature of 350 ° C.

The desulfurization / denitrification activity is a relative activity value obtained by setting the rate constant of the catalyst F of Comparative Example 1 described later as 100.

The rate order of the desulfurization activity is Km when the desulfurization reaction rate is proportional to the 1.75th power of the sulfur concentration of the feedstock.
= LHSV · (1 / n−1) · {(1 / S ⁿ⁻¹ ) − (1
/ So ^n-1 )}.

The rate order of the denitrification activity is defined as K in which the denitrification reaction rate is proportional to the 1.0th power of the nitrogen concentration in the feed
It was determined using the formula of m = LHSV · 1n (No / N).

In the equation, n is the velocity order, LHSV is the liquid hourly space velocity, S is the sulfur concentration in the treated oil (%), So is the sulfur concentration in the feed oil (%), and N is the nitrogen concentration in the treated oil ( %), No
Is the nitrogen concentration (%) in the feed oil.

The sulfur content of the treated oil was analyzed by SLFA-920 model manufactured by Horiba Ltd., and the nitrogen content was analyzed by TN-05 model manufactured by Mitsubishi Kasei.

Catalyst A had a desulfurization activity of 121% and a denitrification activity of 122%. It is clear that the catalyst A has excellent desulfurization / denitrification activity as compared with the catalyst F of Comparative Example 1 prepared according to the conventional method for producing a hydrotreated molten catalyst described below.

(Examples 2 to 4) Molybdenum trioxide 122
g, nickel carbonate 49 g, 85% phosphoric acid 44 g and water were heated and dissolved, and a solution in which the amounts of diethylene glycol added were changed to 27 g, 113 g and 226 g, respectively, and β-thiodiglycol 86 g were added respectively. Catalysts B, C and D were obtained in substantially the same manner as the catalyst A shown in Example 1 except that kneading was performed. The metal content of each of the catalysts B, C, and D was 18% by weight as MoO ₃ , 4% by weight as NiO, and 4% by weight as P ₂ O ₅ , and the addition amount of diethylene glycol was the number of metal moles of molybdenum and nickel. 0.125 times, 0.50 times, 1.0 times, and β-
The amount of thiodiglycol added is 0. 1 which is the amount necessary for molybdenum and nickel to form MoS ₂ and NiS, respectively.
It was three times.

Further, a part of each of the catalysts B, C and D is added to 5
The total pore volumes measured by nitrogen adsorption method after firing at 00 ° C. for 2 hours were 0.45 ml / g and 0.49 ml / g, respectively.
g, 0.52 ml / g, the average pore diameters are 78 Å, 85 Å, 93 Å, and the pore volume in the range of the average pore diameter ± 10 Å is 63% of the total pore volume. ,
It was 60% and 60%. The activity evaluation was performed in the same manner as in the method described in Example 1. The desulfurization activities of catalysts B, C and D are 121%, 119% and 120%, respectively.
The denitrification activities are 120%, 121%, and 118, respectively.
%Met.

(Example 5) 122 g of molybdenum trioxide,
Catalyst shown in Example 1 except that 49 g of nickel carbonate, 44 g of 85% phosphoric acid and water were dissolved by heating, and a solution of 80 g of triethylene glycol and 86 g of β-thiodiglycol were added and kneaded. A catalyst E was obtained in the same manner as in A.

The metal content of catalyst E is 1 as MoO _3.
8% by weight, 4% by weight as NiO and 4% by weight as P ₂ O ₅ , the amount of triethylene glycol added was 0.25 times the number of moles of metal molybdenum and nickel, and β-thiodiglycol was added. The amount is 0.3, which is the amount required for molybdenum and nickel to form MoS ₂ and NiS, respectively.
It was double. Further, the total pore volume measured by the nitrogen adsorption method after part of the catalyst E was calcined at 500 ° C. for 2 hours was 0.48.
ml / g, the average pore diameter was 82 Å, and the pore volume in the range of the average pore diameter ± 10 Å was 62% of the total pore volume. Also,
The activity evaluation was carried out in the same manner as in the method described in Example 1.
Catalyst E is a catalyst in which triethylene glycol is added instead of diethylene glycol, but the desulfurization activity is 12
It is clear that at 1%, the denitrification activity is 120%, which is equivalent to that of catalyst A.

Comparative Example 1 3000 g of an alumina hydrate cake (750 g as Al ₂ O ₃ ) obtained by a method similar to the method for producing an alumina hydrate cake shown in Example 1 was placed in a kneader with a heating jacket. After kneading while heating at 70 ° C and sufficiently plasticizing, it is molded with an extrusion molding machine equipped with a die having a diameter of 1.7 mm, and it is molded at 100 ° C for 15 minutes.
It was dried for an hour and calcined at 600 ° C. for 2 hours to obtain a γ-alumina carrier.

Next, 500 g of the carrier was impregnated with a solution of 390 ml obtained by heating and dissolving 122 g of molybdenum trioxide, 49 g of nickel carbonate, 44 g of 85% phosphoric acid and water, and then drying at 100 ° C. for 15 hours, A catalyst F was obtained by calcining at 500 ° C. for 2 hours.

The metal content of the catalyst F is 1 as MoO _3.
8% by weight, 4% by weight as NiO and 4% by weight as P ₂ O ₅ , and the total pore volume measured by the nitrogen adsorption method was 0.51.
ml / g, the average pore diameter was 84 Å, and the pore volume in the range of the average pore diameter ± 10 Å was 65% of the total pore volume. Further, the activity evaluation was carried out in a fixed bed flow reactor with a catalyst loading of 15 ml, containing 2.5% by weight of hydrogen and dimethyldisulfide.
The added light oil was supplied under the conditions of hydrogen / oil supply ratio of 200 Nl / l, liquid space velocity of 2.0 hr ^-1 , pressure of 30 kg / cm ² G 1
The temperature was raised from 00 ° C to 315 ° C over 7 hours, and after presulfiding for 16 hours, a quat atmospheric gas oil containing 1.15 wt% of sulfur and 68 wtppm of nitrogen was used and the pressure was 30 kg /
cm ² G, liquid hourly space velocity 2.0 hr ^-1 , hydrogen / oil supply ratio 2
The reaction was carried out under the reaction conditions of 00 Nl / l and a temperature of 350 ° C. Catalyst F was obtained according to a conventional method for producing a catalyst, and the desulfurization activity and denitrification activity of this catalyst were set to 100.

(Comparative Example 2) Al ₂ O ₃ was obtained without adding gluconic acid at a concentration of 50% under the hydrolysis condition of alumina.
A catalyst G was obtained in substantially the same manner as in Example 1 except that the aluminum sulfate aqueous solution containing 1 wt% and the sodium aluminate aqueous solution containing 18.4 wt% as Al ₂ O ₃ were all mixed.

The metal content of the catalyst G is 1 as MoO _3.
8% by weight, 4% by weight as NiO and 4% by weight as P ₂ O ₅ , the addition amount of diethylene glycol was 0.25 times the metal mole number of molybdenum and nickel, and the addition amount of β-thiodiglycol was Molybdenum and nickel were 0.3 times the amounts required to form MoS ₂ and NiS, respectively. Moreover, after part of the catalyst G was calcined at 500 ° C. for 2 hours, the total pore volume measured by the nitrogen adsorption method was 0.64.
ml / g, the average pore diameter was 90 Å, and the pore volume in the range of the average pore diameter ± 10 Å was 40% of the total pore volume. further,
The activity evaluation was carried out in the same manner as in the method described in Example 1.
Catalyst G has a large pore volume after calcination at 500 ° C. for 2 hours and a wide pore distribution, so that the desulfurization activity of this catalyst is 109% and the denitrification activity is 107%, which is lower than that of catalyst A. Indicated.

(Examples 6 to 8) Molybdenum trioxide 122
g, cobalt carbonate 45 g, 85% phosphoric acid 44 g and water, and molybdenum trioxide 127 g, cobalt carbonate 82 g, 8
5% phosphoric acid 46g, water, and molybdenum trioxide 208
g, 51 g of cobalt carbonate, 50 g of 85% phosphoric acid, and water were dissolved by heating, and 54 g, 61 g, and 71 g of diethylene glycol were added to each solution, and β-thiodiglycol was added to 86 g, and kneaded. Except for the above, Catalysts I, J, and K were obtained by a method similar to that of Catalyst A shown in Example 1.

The metal content of catalyst I is 1 as MoO _3.
8% by weight, CoO 4% by weight, P ₂ O ₅ 4% by weight, and the metal content of the catalyst J is 18 as MoO _3.
% By weight, 7% by weight as CoO, 4% by weight as P ₂ O ₅
The metal content of the catalyst K was 27% by weight as MoO ₃ , 4% by weight as CoO and 4% by weight as P ₂ O ₅ . The amount of diethylene glycol added was 0.25 times the number of moles of metal of molybdenum and cobalt, and the amount of β-thiodiglycol added was 0.5 times the amounts required for molybdenum and cobalt to form MoS ₂ and CoS, respectively. Three
It was double. In addition, a part of each of the catalysts I, J and K is added to
The total pore volumes measured by the nitrogen adsorption method after firing at 00 ° C. for 2 hours were 0.50 ml / g and 0.49 ml / g, respectively.
g, 0.46 ml / g, the average pore diameters are 80 Å, 81 Å, and 84 Å, respectively, and the pore volume in the range of the average pore diameter ± 10 Å is 62% of the total pore volume. ,
It was 62% and 62%. The activity evaluation was performed in the same manner as in the method described in Example 1.

Catalysts I, J, and K are catalysts in which cobalt is added as an active metal in place of change in molybdenum content and nickel, but desulfurization activities are 128% and 126, respectively.
%, 132%, denitrification activity is 116%, 11
Although 9% and 117%, which are somewhat inferior to the catalyst A in denitrification activity, it is clear that cobalt may be used as the active metal instead of nickel.

(Examples 9 to 10) Catalysts L and M were obtained in substantially the same manner as the catalyst A shown in Example 1 except that the amount of β-thiodiglycol added was changed to 43 g and 143 g.

The metal content of the catalysts L and M was 18% by weight as MoO ₃ , 4% by weight as NiO and 4% as P ₂ O _5.
% By weight, the amount of diethylene glycol added is 0.25 times the number of moles of molybdenum and nickel, and β-
The amount of thiodiglycol added is the amount of catalyst L required for molybde and nickel to form MoS ₂ and NiS, respectively.
Was 0.15 times and catalyst M was 0.5 times.

Further, a part of each of the catalysts L and M is 500
The total pore volume measured by the nitrogen adsorption method after calcination at 2 ° C. for 2 hours is 0.47 ml / g and 0.53 ml / g, the average pore diameter is 79 angstroms and 83 angstroms, and the average pores are Pore volume within diameter ± 10 Å is 62%, 60% of total pore volume
Met. The activity evaluation was performed in the same manner as in the method described in Example 1.

Catalyst L is a catalyst in which the amount of β-thiodiglycol added is smaller than that of catalyst A, but the desulfurization activity is 120.
%, The denitrification activity is 119%, which is somewhat inferior to the catalyst A in desulfurization and denitrification activity, but the addition amount of β-thiodiglycol is the amount necessary for molybdenum and nickel to form MoS ₂ and NiS, respectively. It is clear that even with 0.15 times, it has sufficient performance.

Further, the catalyst M is a catalyst in which the amount of β-thiodiglycol added is larger than that of the catalyst A, but the desulfurization activity is 1
It has 22% and a denitrification activity of 120%, which is almost the same as desulfurization / denitrification activity of catalyst A. The addition amounts of β-thiodiglycol are MoS ₂ and N respectively.
It is also clear that even 0.5 times the amount required to form iS does not dramatically improve the activity.

[0050]

EFFECTS OF THE INVENTION The hydrodesulfurization / denitrification catalyst of the present invention can perform hydrodesulfurization / denitrification of hydrocarbon oil extremely efficiently as compared with conventionally proposed hydrodesulfurization / denitrification catalysts. it can. Therefore, the catalyst of the present invention can be used as a conventional catalyst without being subjected to a complicated pre-sulfurization treatment, and a fuel oil having a low sulfur content and a low nitrogen content can be produced.

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[Procedure amendment]

[Submission date] January 26, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 3

[Correction method] Change

[Correction content]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location // C07B 61/00 300

Claims (3)

[Claims] 1. An alumina hydrate having a pseudo-boehmite structure, an aqueous hydrogenation active metal solution belonging to a metal of Group 6 and a metal of Group 8 of the periodic table, phosphoric acid, a polyhydric alcohol, and an organic sulfur. A method for producing a catalyst for hydrotreating a hydrocarbon oil, comprising adding a compound, kneading, molding, and then drying at a temperature of 150 ° C. or lower. 2. The method for producing a catalyst for hydrotreating hydrocarbon oil according to claim 1, wherein the oxide conversion amount of molybdenum of the 6th metal of the periodic table is equivalent to the oxide conversion amount of alumina hydrate. 15 to 30% by weight, the equivalent oxide of nickel and / or cobalt of Group 8 metal is 3 to 8% by weight, the equivalent oxide of phosphoric acid is 2 to 8% by weight, and polyvalent Diethylene glycol and / or triethylene glycol of alcohol are added in an amount of 0.1 to 1 times the total molar amount of Group 6 metal and Group 8 metal of the periodic table, and β-thiodiglycol of the organic sulfur compound is added. The method according to claim 1, wherein the amount of addition of the Group 6 metal and the Group 8 metal of the periodic table is 0.1 times or more the amount required for forming the sulfide form. 3. A catalyst for hydrotreating a hydrocarbon oil produced by the production method according to claim 1 or 2, wherein:
After the catalyst dried at a temperature of 0 ° C or lower was calcined at 500 ° C, the total pore volume measured by the nitrogen adsorption method was 0.6 ml / g.
The average pore diameter is 80 to 100 angstroms, and the pore volume in the range of the average pore diameter ± 10 angstroms is 60% or more of the total pore volume. Hydrotreating catalyst.