JPH07299364A - Catalyst for hydrodesulfurization and denitrification and its production - Google Patents

Abstract

PURPOSE:To obtain a catalyst having a sufficient hydrodesulfurization and denitrification activity against hydrocarbon oil and capable of being efficiently produced by a simple catalyst production method. CONSTITUTION:A soln. of a hydrogenating active metal belonging to group VIa, VIII metals as an active metal component and a polyhydric alcohol are added to a compsn. consisting of boria and alumina and the resultant mixture is kneaded and molded to be dried at 150 deg.C or lower.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrotreating catalyst capable of effectively removing both sulfur compounds and nitrogen compounds contained in hydrocarbon oil.
Hydrodesulfurization used to reduce both sulfur and nitrogen contents in feedstock hydrocarbon oil by treating hydrocarbon oil containing sulfur compounds and nitrogen compounds under hydrogen pressure and converting to hydrogen sulfide and ammonia 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 of hydrotreating by contacting the hydrocarbon oil under a high temperature and high pressure reaction condition in the presence of hydrogen. It has been known. The hydrodesulfurization method is one of the hydrotreating methods, and as the hydrotreating catalyst, a catalyst in which a metal of Group VIa and a metal of Group VIII of the Periodic Table are supported on a porous alumina carrier is generally used. ing. However, these hydrocatalysts have high activity for hydrodesulfurization reaction and can be economically processed by reducing hydrogen consumption. On the other hand, for hydrodenitrogenation reaction, It did not show sufficient activity.

That is, under normally used hydrodesulfurization conditions, the hydrodenitrogenation activity becomes remarkably lower than the hydrodesulfurization activity. Therefore, in order to sufficiently carry out the hydrodenitrogenation reaction using the hydrodesulfurization denitrification catalyst,
It is necessary to carry out the treatment at higher temperature and pressure or at a lower space velocity. However, when the hydrocarbon oil is actually hydrotreated under such conditions, satisfactory results can be obtained for hydrodenitrogenation, while desulfurization or hydrogenation or lightening cannot be performed. Go beyond need,
As a result, hydrogen consumption is significantly increased, which is not only economically unfavorable but also impractical.

Therefore, in order to hydrotreate a hydrocarbon oil to remove sulfur compounds and nitrogen compounds at the same time, in addition to the conventionally known hydrodesulfurization activity, the C--N bond is cleaved. It is desired to develop a catalyst that also has hydrodenitrogenation activity so as to obtain it. Various studies have been conducted on catalysts having both hydrodesulfurization and denitrification activities, and some proposals have been made as described below.

For example, US Pat. No. 3,749,664 describes a catalyst in which molybdenum, nickel or cobalt and phosphorus are supported on an alumina or silica-alumina carrier in a specific ratio, and the carrier is Generally 0.
It is described that the one having a pore volume of 6 to 1.4 cc / g is preferable, but the pore structure has not been sufficiently examined and is satisfactory for the hydrotreatment of hydrocarbon oil. It does not have the performance to obtain.

In US Pat. No. 3,954,670 or Japanese Patent Laid-Open No. 51-100983, the periodic table VIa is used.
It has been described that a catalyst consisting of a Group VIII metal and a Group VIII metal of the Periodic Table and alumina and boria is effective for the hydrodenitrogenation reaction. However, with regard to this catalyst as well, the composition and the pore characteristics have been sufficiently investigated. No mention is made of hydrodesulfurization reaction.

Japanese Unexamined Patent Publication No. 4-156949 discloses a carrier material containing, as a main component, one or both of an inorganic oxide and an inorganic hydrate, an active metal such as cobalt, nickel, molybdenum and tungsten, a hydroxycarboxylic acid and a phosphoric acid. After adding an aqueous solution containing, kneading and molding,
Disclosed is a method for producing a hydrotreating catalyst, which comprises drying at the following temperature. However, this publication only mentions desulfurization performance, no specific description regarding denitrification performance is found, and no mention is made of the pore characteristics of the catalyst.

Further, in Japanese Patent Laid-Open No. 4-166233, an active metal is supported on an inorganic oxide carrier and then dried,
A method for producing a catalyst by further supporting a polyhydric alcohol or the like on a calcined catalyst and drying and a method for producing a catalyst by supporting a polyhydric alcohol or the like on a dried catalyst after supporting an active metal and drying the catalyst have been proposed. However, the inorganic oxide carrier is alumina, and its characteristics are not described at all. Moreover, in this method for producing a catalyst, there is a problem that the production process becomes extremely complicated because the polyhydric alcohol is loaded after the active metal is loaded and then dried or calcined.

[0009]

As described above, in the conventional catalysts, many catalyst carriers containing alumina or silica as a main component or improved catalysts thereof were used. The catalysts proposed in (1) have been devised in various ways to perform desulfurization activity and denitrification activity in the hydrotreating reaction, but they have not been sufficient yet.

The inventors of the present invention focused on increasing the melting point of the carrier which is the base of the catalyst, and after setting the composition ratio of the carrier composed of boria and alumina within a specific range and the effective pore diameter within a specific range. A hydrodesulfurization and hydrogenation by using a catalyst obtained by impregnating and supporting a metal of group VIa of the periodic table, a metal of group VIII of the periodic table and a polyhydric alcohol as a hydrogenation-active metal on the carrier and using the dried substance as a catalyst. It was found that both activities of denitrification are improved (Japanese Patent Application No. 5-23505).
issue).

The present invention solves the above-mentioned problems of conventional catalysts, has sufficient hydrodesulfurization and denitrification activities of hydrocarbon oil, and is efficiently produced by a simple catalyst production process. The present invention is intended to apply a hydrodesulfurization and denitrification catalyst and a method for producing the same, which can

[0012]

Means for Solving the Problems The present invention for achieving the above object belongs to a group VIa metal and a group VIII metal of the periodic table as an active metal component for a composition consisting of boria and alumina. After adding the hydrogenation active metal solution and the polyhydric alcohol, kneading and molding, and then 150
A method for producing a catalyst for hydrodesulfurization and denitrification, which is characterized by drying at a temperature of ℃ or less, and in the catalyst produced by the above-mentioned production method, the content of boria in the composition comprising boria and alumina is ₃ as B ₂ O 3
15% by weight, the Group VIa metal of the periodic table contained as an active metal component is molybdenum, the group VIII metal of the periodic table is nickel and / or cobalt, and the addition amount of each is the catalyst weight obtained as the final product. On the other hand, molybdenum is 17 to 28 wt% in terms of oxide, nickel and / or cobalt is 3 to 8 wt% in terms of oxide, and polyhydric alcohol is diethylene glycol and / or
Or triethylene glycol, the addition amount of which is 0.2 to 3 times the total molar amount of Group VIa metal of the Periodic Table and Group VIII metal of the Periodic Table, for hydrodesulfurization and denitrification Furthermore, the physical properties of the catalyst when it is calcined at 500 ° C. is 90 to 1 in terms of pore distribution measured by mercury porosimetry.
A catalyst for hydrodesulfurization and denitrification, which has an average pore diameter of 20 Å, and the volume of pores in the range of average pore diameter ± 10 Å is 60% or more of the total pore volume. Is the gist.

[0013]

In the structure of the catalyst for hydrodesulfurization and denitrification according to the present invention, molybdenum is used as the VIa metal of the periodic table as the hydrogenation active metal component to be supported, and the supported amount is 17 to 28% by weight in terms of oxide. And the Periodic Table VI
It is already known that a highly active catalyst can be obtained by adopting nickel and / or cobalt as the group II metal and setting the supported amount thereof to 3 to 8% by weight in terms of oxide. In addition, it has already been known that the catalyst using both cobalt and molybdenum as hydrogenation active metal components has high hydrodesulfurization activity, and the catalyst using both nickel and molybdenum has high hydrodenitrogenation activity. That is what is being done.

The essence of the present invention is that after adding a predetermined amount of hydrogenation active metal and a predetermined amount of polyhydric alcohol to a carrier composition consisting of boria and alumina, kneading and molding, and then 150 ° C. or lower. To produce a catalyst by drying at a temperature of 100 ° C., and when the dried catalyst thus produced is calcined at a temperature of 500 ° C., the physical property of the catalyst is 90 to 120 in terms of average pore diameter. And the volume occupied by pores having an average pore diameter of ± 10 Å is at least 6 of the total pore volume.
It was 0%, and it was found that the dry catalyst finally used as a catalyst has the highest effect on the hydrodesulfurization and denitrification activity when it has such physical properties.

In the carrier composition composed of boria and alumina used in the catalyst of the present invention, when the composition ratio of boria is ₃ to 15% by weight as B ₂ O ₃ , the denitrification activity is dramatically improved. Although the performance is improved, the effect of improving the activity is considered to be due to the acid property of the carrier.

The polyhydric alcohol used in the catalyst of the present invention is preferably diethylene glycol or triethylene glycol, and one or both of them are used, and the addition amount thereof is 0.1% of the molar amount of the hydrogenation active metal.
It is preferably in the range of 2 to 3 times. This addition amount is a necessary amount for reacting with a hydrogenation active metal component to form a complex compound, and if it is added in an amount less than 0.2 times, a sufficient effect cannot be exhibited, and if added in an amount more than 3 times, In the sulfurization step, the polyhydric alcohol contained in excess is not decomposed but remains in the catalyst as carbon, and both hydrodesulfurization and denitrification activities are reduced, which is not preferable in any case.

As the drying temperature of the catalyst of the present invention, a temperature at which the added polyhydric alcohol does not volatilize or decompose may be selected, and drying at a temperature of 150 ° C. or lower is desirable. Also, the dry catalyst according to the present invention may
Regarding the pore diameter and pore distribution in the physical properties of the catalyst after calcination at 0 ° C., the number of pores having a diameter effective for desulfurization and denitrification reactions should be increased as much as possible to suppress other harmful reactions. It is essential that the pore distribution be dense and that the average pore diameter be within a specific range for that purpose, and the carrier pore structure for this purpose is measured by mercury porosimetry. In the pore distribution of, the average pore diameter is in the range of 90 to 120 angstroms, and the volume occupied by the pores in the average pore diameter ± 10 angstrom range is preferably at least 60% of the total pore volume, Desulfurization of the dry catalyst finally obtained at this time,
The effect of denitrification is the best.

When the average pore diameter is smaller than 90 Å, the diffusion resistance of the reactant in the catalyst particles becomes too large, and the hydrodesulfurization / denitrification activities decrease.
On the other hand, when the average pore diameter is larger than 120 angstroms, a large amount of the reactant enters the pores at a time and the carbonaceous material produced by the decomposition thereof precipitates to lower both hydrodesulfurization and denitrification performance. I will let you. Further, when the volume of pores in the range of average pore diameter ± 10 angstrom is 60% or less of the total pore volume, even if the average diameter of pores is in the range of 90 to 120 angstrom. Since both pores effective for the hydrodesulfurization and denitrification reaction of hydrocarbon oil are reduced, both activities are reduced.

The carrier composition consisting of boria and alumina is
For example, it can be manufactured by a known general carrier manufacturing method such as a mixing method. Therefore, in order to produce the catalyst of the present invention, for example, an aluminum sulfate aqueous solution and a sodium aluminate aqueous solution are mixed and hydrolyzed, and the resulting alumina hydrate slurry is filtered and washed to obtain an alumina hydrate, The hydrate has a boria content of _{3 to 1} as B ₂ O _3.
An aqueous solution obtained by adding boric acid to 5% by weight and then adding an organic acid such as citric acid or tartaric acid to a slurry prepared by suspending molybdenum trioxide and nickel carbonate or cobalt carbonate in water and heating and dissolving the mixture. And diethylene glycol and / or triethylene glycol are added, then kneaded until the water content becomes moldable and fully plasticized, then molded into a general catalyst shape such as cylindrical, spherical, trilobal, or four-lobed. Then, it is dried by a conventional method at a temperature of 150 ° C. or lower.

When an organic acid such as gluconic acid or tartaric acid is added during the hydrolysis reaction for obtaining the alumina hydrate,
It is effective for obtaining a catalyst in which the pore distribution is concentrated within a specific range.

Examples of the boria raw material used in producing the carrier composition comprising the boria and alumina include soluble borate salts such as boric acid, tetraboric acid and ammonium borate. Examples include aluminum nitrate, aluminum sulfate, sodium aluminate and the like, and water-soluble salts thereof.

The dried catalyst obtained as described above is put into a reaction tower or the like and subjected to sulfidation treatment as in the case of the catalyst obtained by the conventional production method, and then put to practical use.

The catalyst for hydrodesulfurization and denitrification prepared by the present invention is used for hydrodesulfurization reaction and hydrodenitrogenation reaction of hydrocarbons, in which an oxide support carries an active metal and is dried or calcined after drying. The catalyst obtained by the conventional method for producing a catalyst exhibits a higher activity than that obtained by subjecting the catalyst to sulfurization treatment, but the reason for this is unclear.

That is, if the above-mentioned hydroxycarboxylic acid is used, it is considered that it is due to the formation of a complex ion between the hydroxycarboxylic acid and the active metal, but in the case of the polyhydric alcohol used in the present invention, its coordination is considered. It is hard to think that this is the main reason because the ability is low. Rather, the adsorption rate of the active metal component is weakened in the process of adding polyhydric alcohol and kneading,
This is uniformly dispersed on the surface of the pores of the carrier composition consisting of boria and alumina to be fixed in the drying step, and the metal sulfide generated when the active metal component is changed to the sulfide form in the sulphidizing step to be performed next. It is considered that this is because the agglomeration of the product particles is prevented and the particle size of the sulfide particles is made small and highly dispersed.

[0025]

EXAMPLES Next, in Examples of the present invention, as polyhydric alcohols, diethylene glycol was added (Examples 1 to 5, Comparative Examples 1 to 3) and triethylene glycol was added (Examples 6 to 10). , Comparative Examples 5 to 7) and the case where no polyhydric alcohol was added (Comparative Example 4) will be described. Example 1 In a reaction tank made of stainless steel with an internal volume of 100 liter and equipped with a stirrer, 49.5 liters of water and gluconic acid solution of 50% concentration (manufactured by Wako Pure Chemical Industries, Ltd.) 204 g (Al ₂ O ₃ produced by hydrolysis reaction) 0.05% by weight) to 70 ° C
To 95 ° C, hold at the same temperature and stir while stirring 95% of aluminum sulfate aqueous solution (8% sulfuric acid band sold by Shimada Shoten).
40 g and a sodium aluminate aqueous solution (NA-170 manufactured by Sumitomo Chemical Co., Ltd.) were mixed to obtain an alumina hydrate slurry having a pH of 8.8.

Next, this slurry was aged for 30 minutes and then filtered and washed to obtain 2250 g of alumina hydrate cake (A
l ₂ O ₃ as 450 g) boric acid (manufactured by Wako Pure Chemical Industries, Ltd., reagent first grade) 89 g ₍₅₀ g as B 2 _{O 3)} and molybdenum trioxide 117 g, nickel carbonate 59g was suspended in water 250 g, added tartaric acid 10g And 119 g of diethylene glycol were added and the mixture was heated and kneaded in a kneader with a heating jacket to obtain a kneaded product having a plasticity of 63% by weight as a concentration, and then the kneaded product had a diameter of 1.5 mm.
Molding was carried out using an extrusion molding machine having the above die, and the resulting molded body was dried at 100 ° C. for 18 hours to obtain catalyst A.

The amount of boric acid in terms of oxide of the catalyst A, the active metal content, and the amount of diethylene glycol added to the active metal content, and a part of the catalyst A at 500 ° C.
The physical properties of the catalyst after calcining for 2 hours are also shown in Table 1.

In the evaluation of the catalyst, a hydrodesulfurization reaction activity and a hydrodenitrogenation reaction activity of the hydrocarbon oil were investigated using a solid bed flow reactor having a catalyst loading of 15 ml.

The catalyst sulfurization conditions are as follows. Light oil containing 2.5% by weight of dimethyl disulfide is used and hydrogen / oil supply ratio is 200.
N liter / liter, LHSV = 2.0 hr ⁻¹ , pressure 30 kg / cm ² G 100 ° C. to 315 ° C.
The temperature was raised over 7 hours, and the temperature was maintained at that temperature for pre-sulfurization for 16 hours.

For the evaluation of the catalyst, a normal pressure gas oil produced by Kuate containing 1.15% by weight of sulfur and 68 ppm by weight of nitrogen was used, and the reaction conditions were as follows: pressure 30 kg / cm ² G, LHSV =
2.0 hr ^-1 , hydrogen / light oil supply ratio 300 N liter /
It was carried out at a reaction starting temperature of 360 ° C.

The sulfur content and nitrogen content in the treated oil after 50 hours from the start of the reaction were analyzed to determine the desulfurization activity and denitrification activity, and the results are also shown in Table 1.

The analysis of the sulfur content is shown by the relative activity value of the reaction rate constant when the catalyst O is 100, and the rate order is such that the desulfurization reaction rate is proportional to the 1.75th power of the sulfur concentration of the feedstock. Km = LHSV * (1 / n-1) * {(1 / ^Sn-1 )
It was calculated using the formula − (1 / Son ⁻¹ )}. Here, n is the velocity order 1.7.
5, LHSV is the liquid hourly space velocity (hr ⁻¹ ), S is the sulfur concentration (%) in the treated oil, and So is the sulfur concentration (%) in the feed oil.

The denitrification activity is represented by the relative activity value of the reaction rate constant when the catalyst O is 100, and the rate order is proportional to the denitrification reaction rate to the 1.0th power of the nitrogen concentration in the feedstock. As a result, it was obtained by using the equation Km = LHSV · 1n (No / N). Here, LHSV is the liquid hourly space velocity (hr ⁻¹ ), No is the nitrogen concentration (%) in the treated oil, N
Is the nitrogen concentration in the feed oil. Example 2 Alumina hydrate obtained in the same manner as in Example 1 was treated with Al.
Against ₂ O ₃ in terms amounts, 3 _wt% the amount of boric acid as a _B 2 _{O 3} to be _added, except for changing the B 2 _{O 3} to 15 wt% in substantially the same manner as the method shown in Example 1 To obtain catalyst B and catalyst C.

The amount of boric acid in terms of oxide of catalyst B and catalyst C, the active metal content, and the amount of diethylene glycol added to the active metal content, and a part of catalyst B and catalyst C were each 500 ° C. Table 1 also shows the physical properties and activity evaluation results of the catalyst after calcining for 2 hours. Example 3 Addition The amount of the active metal added and kneaded was adjusted to 19
9 g, nickel carbonate 67 g and molybdenum trioxide 11
Example 1 except that the amount was changed to 7 g and nickel carbonate 83 g.
Catalyst D and catalyst E were obtained in substantially the same manner as in the above.

The amounts of boric acid converted to oxides of catalyst D and catalyst E, the active metal content, and the amount of diethylene glycol added to the active metal content, and a part of catalyst D and catalyst E were 500 ° C., respectively. Table 1 also shows the physical properties and activity evaluation results of the catalyst after calcining for 2 hours. Example 4 Catalyst F and catalyst G were obtained in substantially the same manner as in Example 1 except that the amounts of diethylene glycol to be added and kneaded were changed to 56 g and 356 g.

The amounts of boric acid in terms of oxide of the catalysts F and G, the active metal content, and the amount of diethylene glycol added to the active metal content, and a part of the catalysts F and G were 500 ° C., respectively. Table 1 also shows the physical properties and activity evaluation results of the catalyst after calcining for 2 hours. Example 5 Cobalt carbonate was used instead of nickel carbonate as an active metal component to be added and kneaded, and the active metal was added in an amount of 117 g of molybdenum trioxide, 54 g of cobalt carbonate, 199 g of molybdenum trioxide, 61 g of cobalt carbonate, and 117 g of molybdenum trioxide. Catalysts H, I, and J were obtained in substantially the same manner as in Example 1, except that 7 g of cobalt carbonate was used.

The amounts of boric acid converted to oxides of catalysts H, I, and J, the active metal content, and the amount of diethylene glycol added to the active metal content, and the catalysts H, I, and
Table 1 also shows the physical properties and activity evaluation results of the catalyst after part of J was calcined at 500 ° C. for 2 hours. Comparative Example 1 A catalyst K was obtained in substantially the same manner as in Example 1 except that boric acid to be added and kneaded was not added.

The amount of boric acid in terms of oxide of the catalyst K, the active metal content, and the amount of diethylene glycol added to the active metal content, and a part of the catalyst K are 500
Table 1 also shows the physical properties and activity evaluation results of the catalyst after calcination for 2 hours. Comparative Example 2 Example 1 except that gluconic acid was not added to the reaction tank.
A catalyst L was obtained in substantially the same manner as the method shown in.

The amount of boric acid in terms of oxide of the catalyst L, the active metal content, and the amount of the diethylene glycol added to the active metal content, and a part of the catalyst L are 500
Table 1 also shows the physical properties and activity evaluation results of the catalyst after calcination for 2 hours. Comparative Example 3 Alumina hydrate obtained in the same manner as in Example 1 was replaced with Al.
The added amount of boric acid to be added is B based on the amount converted to ₂ O _3.
Catalyst M and catalyst N were obtained in the same manner as in Example 1 except that the amount of ₂ O ₃ was changed to 20% by weight.

The amounts of boric acid converted to oxides of the catalyst M and the catalyst N, the active metal content, and the amount of diethylene glycol added to the active metal content, and a part of the catalyst M and the catalyst N were each 500 ° C. Table 1 also shows the physical properties and activity evaluation results of the catalyst after calcining for 2 hours. Comparative Example 4 A catalyst O was obtained in substantially the same manner as in Example 1 except that ethylene glycol to be added and kneaded was not added.

Table 1 shows the boric acid content and active metal content in terms of oxide of the catalyst O, the physical properties of the catalyst O after burning a part of the catalyst O for 2 hours at 500 ° C., and the results of activity evaluation.

[0042]

[Table 1]

Example 6 As a polyhydric alcohol to be added and kneaded, a catalyst P was obtained in substantially the same manner as in Example 1 except that triethylene glycol was used instead of diethylene glycol and the addition amount was 167 g. .

The amount of boric acid converted to the oxide of the catalyst P, the active metal content, the amount of triethylene glycol added to the active metal content, and a part of the catalyst P were 500
Table 2 also shows the physical properties and activity evaluation results of the catalyst after calcination for 2 hours. Example 7 A catalyst Q and a catalyst R were obtained in substantially the same manner as in Example 2 except that triethylene glycol was used instead of diethylene glycol as the polyhydric alcohol to be added and kneaded, and the addition amount was 167 g. .

The amounts of boric acid converted to oxides of the catalyst Q and the catalyst R, the active metal content, the amount of triethylene glycol added to the active metal content, and a part of the catalyst Q and the catalyst R were 500, respectively. Table 2 also shows the physical properties and activity evaluation results of the catalyst after calcination for 2 hours. Example 8 As a polyhydric alcohol to be added and kneaded, a catalyst S and a catalyst T were obtained in substantially the same manner as in Example 3 except that triethylene glycol was used instead of diethylene glycol and the addition amount was 167 g. .

The amount of boric acid in terms of oxide of the catalyst S and the catalyst T, the active metal content, the double amount of the added triethylene glycol based on the active metal content, and a part of the catalyst S and the catalyst T are 500, respectively. Table 2 also shows the physical properties and activity evaluation results of the catalyst after calcination for 2 hours. Example 9 As a polyhydric alcohol to be added and kneaded, catalyst U and catalyst V were prepared in substantially the same manner as in Example 4 except that triethylene glycol was used instead of diethylene glycol and the addition amounts were 84 g and 502 g. Obtained.

The amount of boric acid in terms of oxide of the catalyst U and the catalyst V, the active metal content, the amount of triethylene glycol added to the active metal content, and a part of the catalyst U and the catalyst V were 500, respectively. Table 2 also shows the physical properties and activity evaluation results of the catalyst after calcination for 2 hours. Example 10 Catalysts W, X and Y were obtained in substantially the same manner as in Example 5 except that triethylene glycol was used instead of diethylene glycol as the polyhydric alcohol to be added and kneaded, and the addition amount was 167 g. It was

The amounts of boric acid converted to oxides of the catalysts W, X, and Y, the active metal content, and the amount of triethylene glycol added to the active metal content, and the catalysts W, X,
Table 2 also shows the physical properties and activity evaluation results of the catalyst after part of Y was calcined at 500 ° C. for 2 hours. Comparative Example 5 A catalyst Z was obtained in substantially the same manner as in Comparative Example 1 except that triethylene glycol was used instead of diethylene glycol as the polyhydric alcohol to be added and kneaded, and the addition amount was 167 g.

The amount of boric acid converted to the oxide of the catalyst Z, the active metal content, the amount of triethylene glycol added to the active metal content, and a part of the catalyst Z were 500.
Table 2 also shows the physical properties and activity evaluation results of the catalyst after calcination for 2 hours. Comparative Example 6 A catalyst AA was obtained in substantially the same manner as in Comparative Example 2 except that triethylene glycol was used instead of diethylene glycol as the polyhydric alcohol to be added and kneaded, and the addition amount was 167 g.

The amount of boric acid converted to oxide of the catalyst AA, the active metal content, the amount of triethylene glycol added to the active metal content, and a part of the catalyst AA were 5
Table 2 also shows the physical properties and activity evaluation results of the catalyst after calcining at 00 ° C. for 2 hours. Comparative Example 7 Catalyst AB and catalyst AC were obtained in substantially the same manner as in Comparative Example 3 except that triethylene glycol was used instead of diethylene glycol as the polyhydric alcohol to be added and kneaded, and the addition amount was 167 g. .

The amounts of boric acid and the active metal content in terms of oxides of the catalysts AB and AC, and the double amount of triethylene glycol added to the active metal content, and a part of the catalysts AB and AC were respectively 500 Table 2 also shows the physical properties and activity evaluation results of the catalyst after calcination for 2 hours.

[0052]

[Table 2]

As shown in the results of Tables 1 and 2, the catalysts A, B and C or the catalysts P, Q and R are the contents of molybdenum and nickel converted to oxides and the addition amounts of diethylene glycol or triethylene glycol. ,
The composition ratio of boria and alumina converted to oxide, the average pore diameter and the pore distribution in the physical properties of the catalyst after firing the dried catalyst at 500 ° C. for 2 hours are all within the scope of the present invention. It can be seen that the catalyst exhibits high desulfurization and denitrification activities.

The catalyst D and the catalyst E or the catalyst S and the catalyst T are, respectively, the composition ratio of boria and alumina in terms of oxide, the addition amount of diethylene glycol or triethylene glycol, and the catalyst after firing the dried catalyst at 500 ° C. for 2 hours. In terms of physical properties, the average pore diameter and pore distribution satisfy the scope of the present invention, but regarding the molybdenum and nickel contents converted to oxides, the catalyst D or the catalyst S is the catalyst, respectively. The amount of molybdenum is increased as compared with A or the catalyst P, and the catalyst E or catalyst T is increased with nickel as compared with the catalyst A or the catalyst P, respectively. However, it is understood that both catalysts have sufficiently high desulfurization activity and denitrification activity because they are within the scope of the present invention.

Catalyst F and G or catalyst U and catalyst V
Is the content of the active ingredient in terms of oxide, the addition amount of diethylene glycol, the composition ratio of boria and alumina in terms of oxide, and the average pore diameter in the physical properties after firing the dried catalyst at 500 ° C. for 2 hours. Regarding the pore size distribution, it falls within the scope of the present invention, and the addition amount of diethylene glycol or triethylene glycol is changed from those in the above-mentioned Examples, but this catalyst F and catalyst G, or catalyst U and catalyst The desulfurization activity and denitrification activity of V show the same values as those of the catalyst A or the catalyst P, respectively, and the addition amount of diethylene glycol or triethylene glycol is 0.25 to the molar amount of the active metal.
It can be seen that high activity is exhibited in any case within the range of 1.5 times.

The catalysts H, I, J or the catalysts W, X, Y are
The composition ratio of boria to alumina converted into oxide, the content of active metal, the amount of diethylene glycol or triethylene glycol added, and the physical properties of the catalyst after the dried catalyst was calcined at 500 ° C. for 2 hours showed that the average pore diameter and the fine pore diameter were small. The pore distribution falls within the scope of the present invention and contains molybdenum and cobalt as active metal components. From these results, it is clear that even when cobalt is used instead of nickel, both desulfurization activity and denitrification activity are high.

The catalyst K or the catalyst Z is the content of the active ingredient in terms of oxide, the addition amount of diethylene glycol or triethylene glycol, and the dry catalyst of 50, respectively.
Regarding the average pore diameter and the pore distribution in the physical properties of the catalyst after calcination at 0 ° C. for 2 hours, both fall within the scope of the present invention, but the desulfurization activity is not due to the absence of boria in the components. Excellent, but low in denitrification activity.

The catalyst L or the catalyst AA is within the scope of the present invention with respect to the content of the active ingredient in terms of oxide, the addition amount of diethylene glycol or triethylene glycol, and the composition ratio of boria and alumina in terms of oxide. However, in the physical properties of the catalyst after calcining the dried catalyst at 500 ° C. for 2 hours, the average pore diameter ± 10 angstrom pore volume / total pore volume (%) value is only 45%, and the pore distribution is Since the catalyst L or the catalyst AA is not dense, the desulfurization activity and denitrification activity of the catalyst L or the catalyst AA are lower than those of the catalyst A or the catalyst P having a fine pore distribution.

The catalyst M and the catalyst N or the catalyst AB and the catalyst AC are, respectively, the average pore diameter and the pore distribution in the physical properties of the catalyst after calcining the dried catalyst at 500 ° C. for 2 hours, the oxide-converted active component. The content of C and the addition amount of diethylene glycol or triethylene glycol are both within the range of the present invention, but since the composition ratio of boria to alumina converted to oxide is outside the range of the present invention, the catalyst M and the catalyst The desulfurization activity and denitrification activity of N or the catalyst AB and the catalyst AC are lower than those of the catalyst A or the catalyst P.

As the catalyst O, the composition ratio of boria and alumina in terms of oxide, active metal content, and dry catalyst of 500 were used.
The physical properties of the catalyst after calcination at 2 ° C for 2 hours are within the scope of the present invention with respect to the average pore diameter and the pore distribution, but the polyhydric alcohol is not added, and the desulfurization of this catalyst is performed. Although the activity and the denitrification activity are not always satisfactory, each of them was set to 100 and used as a reference value for performance evaluation in other examples to which the polyhydric alcohol was added.

[0061]

As described above, the catalyst for hydrodesulfurization and denitrification of the present invention is obtained by adding and kneading a polyhydric alcohol together with an active metal to a specific carrier composition, molding and drying,
Compared to the conventionally proposed catalysts for hydrodesulfurization and denitrification, it is possible to cause desulfurization and denitrification reactions more efficiently. Therefore, by using the catalyst of the present invention in place of the conventional catalyst for hydrodesulfurization and denitrification, it becomes possible to efficiently produce fuel oil having a low sulfur content and a low nitrogen content, and such effects are great. .

Claims (3)

[Claims] 1. A composition comprising boria and alumina is added with an aqueous solution of a hydrogenating active metal belonging to Group VIa metal of the Periodic Table and Group VIII metal as an active metal component and a polyhydric alcohol, A method for producing a catalyst for hydrodesulfurization and denitrification, which comprises kneading, molding, and then drying at a temperature of 150 ° C. or lower. 2. A catalyst produced by the method for producing a catalyst for hydrodesulfurization and denitrification according to claim 1, wherein the composition of boria and alumina has a content of boria of B ₂ O.
₃ is ₃ to 15% by weight, the Group VIa metal of the Periodic Table contained as the active metal component is molybdenum, the Group VIII metal of the Periodic Table is nickel and / or cobalt, and the addition amount of each is the catalyst weight. On the other hand, molybdenum is 17 to 28 wt% in terms of oxide, nickel and / or cobalt is 3 to 8 wt% in terms of oxide,
The polyhydric alcohol is diethylene glycol and / or triethylene glycol, and the addition amount thereof is 0.2 to 3 times the total molar amount of the Group VIa metal of the periodic table and the group VIII metal of the periodic table. A catalyst for hydrodesulfurization and denitrification. 3. The physical properties of the catalyst when the dried catalyst is calcined at 500 ° C. has an average pore diameter of 90 to 120 angstrom in pore distribution measured by mercury porosimetry,
The catalyst for hydrodesulfurization and denitrification according to claim 2, wherein the volume of pores having an average pore diameter of ± 10 angstrom is 60% or more of the total pore volume.