JPH11262665A - Catalyst for hydrogenation treating, and method for hydrogenation treating hydrocarbon oil by using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide both high desulfurization activity and high denitrification activity by specifying the weight proportions of boria and silica in a carrier and satisfying specified relation formulae. SOLUTION: The catalyst has a boria-silica-alumina carrier based on silica- alumina and contg. boria. The content of silica as SiO2 and the content of boria as B2 O3 are 2-40 wt.% and 0.1-10 wt.%, respectively, based on the total weight of the carrier. The carrier has a specified pare structure and satisfies the formulae PV(30-100) /PV(0-300) >=0.5 and PV(150-300) /PV(0-300) <=0.4 measured by the nitrogen adsorption method. In the formulae, PV(n-m) is pore volume occupied by pores having n to mÅ pore diameter. The ratio of the volume of pores of 0-300 Å diameter measured by the nitrogen adsorption method to the volume of pores of >=40 Ådiameter measured by the mercury penetration method is >=0.7. The carrier has >=200 m<2> /g specific surface area. When the catalyst is used, hydrocarbon oil such as vacuum light oil or cracked light oil can be hydrogenation treated at a high desulfurization rate and a high denitrification rate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrotreating catalyst and a method for hydrotreating a hydrocarbon oil using the hydrotreating catalyst. More specifically, a hydrotreating catalyst composed of boria-silica-alumina and having a hydrogenation active component supported on a catalyst carrier having a specific pore structure, and the hydrotreating catalyst are used. And a method for hydrotreating hydrocarbon oils for hydrodesulfurization, hydrodenitrogenation, hydrocracking, hydrodearomatization, hydrorefining, etc. of hydrocarbon oils.

[0002]

2. Description of the Related Art Conventionally, hydrocarbon oil has been hydrotreated in a petroleum product manufacturing process. For this purpose, a refractory inorganic oxide such as alumina, silica-alumina, magnesia, and zirconia is used as a carrier, and hydrogen containing a metal of Group 6B or Group 8 of the periodic table as an oxide or sulfide is used. Various catalysts for hydrotreating have been developed. Hydrodesulfurization, hydrodenitrogenation, hydrocracking and hydrocracking and hydrodearomatization of distillate and residual oil of atmospheric or vacuum distillation of petroleum crude oil, and lubricating oil fraction It has been used for hydrorefining and hydroisomerization of wax fractions.

On the other hand, in recent years, further hydrotreating of hydrocarbon oils has been required from the viewpoint of environmental protection. However, conventional hydrotreating catalysts focus on improving the desulfurization activity,
Development of high specific surface area catalysts whose average pore diameter is controlled within a relatively small pore diameter range has been focused on. On the other hand, the denitrification activity for removing nitrogen compounds in fuel oil, which is considered to be a source of nitrogen oxides as a cause of air pollution, was insufficient. When hydrocarbon oils containing these nitrogen compounds are subjected to catalytic cracking or catalytic reforming in the petroleum refining process, the nitrogen compounds significantly lower the activity of the cracking catalyst or reforming catalyst, and the product yield There has been a problem of causing a decrease.

[0004] In order to improve the hydrotreating activity,
Increasing the pore volume of a relatively large pore diameter decreases the specific surface area, and as a result, there is a problem that the hydrogenation active component cannot be highly dispersed and supported on the carrier, and high catalytic activity cannot be obtained. Was. Under such a development situation, development of a hydrotreating catalyst having a high specific surface area which is excellent in desulfurization activity and denitrification activity has been desired.

[0005] For example, Japanese Patent Publication No. 3-31496 discloses that hydrogenation is carried out on a silica-alumina carrier having a specific pore volume and controlled so that pores are distributed in both micropore and macropore regions. A hydrotreating catalyst carrying an active component is described. Also, JP-A-8-89806
The publication discloses that a pore volume having a pore diameter of 60 to 90 ° and a mean pore diameter of ± 10 ° is 60% or more of the total pore volume based on boria-silica-alumina as a substrate. A catalyst for hydrodesulfurization and denitrification in which a hydrogenation active component is supported on a support is described. However, even in these techniques, the activity of the hydrotreating catalyst and the activity maintaining performance thereof were insufficient.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to improve the above-mentioned problems of the prior art and to provide a high desulfurization activity and
An object of the present invention is to provide a catalyst for hydrotreating hydrocarbon oil having high denitrification activity, and a method for hydrotreating hydrocarbon oil using the catalyst for hydrotreating.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a boria-silica-alumina support containing a specific amount of boria has a relatively small pore diameter region and a high pore volume. And found that the hydrotreating catalyst with its pore diameter distribution in a specific range can highly remove both sulfur compounds and nitrogen compounds in hydrocarbon oils, and completed the present invention. Was.

That is, according to the present invention, at least one active ingredient (A) selected from Group 8 elements of the periodic table and a group 6B element of the periodic table are formed on a support comprising boria, silica and alumina. A hydrotreating catalyst carrying at least one selected second active component (B), wherein the boria and the silica are each 0.1 to 10% by weight as B ₂ O ₃ in a carrier. And ₂ to 40% by weight of SiO ₂ and satisfying the following relational expressions (1) to (4).

[0009]

(Equation 2) Further, there is provided a method for hydrotreating a hydrocarbon oil, wherein the hydrocarbon oil is brought into contact with hydrogen in the presence of such a hydrotreating catalyst to highly desulfurize and denitrify. It is.

The present invention relates to a hydrotreating catalyst and a method for hydrotreating a hydrocarbon oil as described above. Preferred embodiments thereof include the following. (1) A hydrotreating catalyst or a hydrotreating method characterized by having the above-mentioned constitutional requirements. (2) The catalyst for hydrotreating or hydrotreating according to (1), wherein the first active component (A) is cobalt, nickel, ruthenium, rhodium, palladium, iridium or platinum. Method. (3) The hydrotreating catalyst or hydrotreating method according to any one of (1) and (2), wherein the second active component (B) is molybdenum or tungsten. (4) The boria is 0.5 to ₇ as B ₂ O _{3 in the} carrier.
The catalyst for hydrotreating or the hydrotreating method according to any one of the above (1) to (3), wherein the catalyst or the hydrotreating method is contained in an amount of 1% by weight. (5) The above-mentioned (1) to (1), wherein the relational expression (1) is: PV _(30-100) / PV _(0-150) ≧ 0.6 to 0.8 (nitrogen adsorption method) The hydrotreating catalyst or hydrotreating method according to any of 4). (6) _Any of the above (1) to (5), wherein the relational expression (2) _satisfies PV _(150-300) / PV _(0-300) ≦ 0.3 (nitrogen adsorption method). 5. The hydrotreating catalyst or hydrotreating method according to any one of the above. (7) The relational expression (3) is

[0011]

(Equation 3) The hydrotreating catalyst or hydrotreating method according to any one of the above (1) to (6), wherein

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. (Hydrotreating catalyst) The hydrotreating catalyst of the present invention is composed of a specific amount of boria, silica, and alumina, and has a specific pore structure on a catalyst support. And at least one second active component (B) selected from Group 6B elements of the periodic table.

The support for the hydrotreating catalyst of the present invention is based on silica-alumina and contains boria as the third component. That is, it has a structure in which silica and boria are dispersed on alumina as a nucleus, and at least two or more atoms of boron, silicon, and aluminum are bonded via an oxygen atom. As a raw material of silica, a silicon compound, for example, an alkali metal silicate (Na ₂ O: SiO ₂ = 1: 2 to 1: 4 is preferable), tetraalkoxysilane, silicon tetrachloride, orthosilicate, or the like is used. be able to. As the raw material of alumina, aluminum compounds, for example, aluminum sulfate, chloride, nitrate, alkali metal aluminate, aluminum alkoxide and other inorganic or organic salts can be used. These aluminum compounds and silicon compounds can be used in an aqueous solution,
And it can be used as a sol-like or gel-like aqueous mixture, and its concentration is not particularly limited and may be appropriately determined. Examples of the boria material include water-soluble salts such as boric acid and ammonium borate.

In the silica-alumina carrier, a relatively strong acid point can be given to the carrier by containing silica in the alumina. The solid acidity of the carrier is preferably controlled by the content of silica. Further, in the boria-silica-alumina carrier, the boria component reduces the strong acid sites of the silica-alumina carrier component and simultaneously increases the weak acid sites to impart a specific acid strength (medium / weak acid) to the carrier. And the activity and selectivity of the catalyst can be improved.

The silica content in the carrier is 2 to 40% by weight, preferably 2 to 20% by weight, based on the total weight of the carrier. If the silica content exceeds 40% by weight, the decomposition of the hydrocarbon oil is promoted, and the hydrotreated oil becomes lighter. The boria content is in the range of 0.1 to 10% by weight based on the total weight of the carrier. Preferably it is 0.5 to 7% by weight. Boria content is 10% by weight
If the ratio exceeds 1, there is a problem that the hydrotreating activity decreases.

It is important that the hydrotreating catalyst of the present invention has a specific pore structure. That is, the hydrotreating catalyst of the present invention has a diameter of 30 measured by the nitrogen adsorption method.
Pore volume occupied by pores in the range of
In order to increase the pore volume occupied by pores in the range of 0 to 150 ° in a well-balanced manner, the pore volume ratio (PV
_{Assuming that (30-100)} / PV _(0-150) ) is X and the pore volume ratio (PV _(150-300) / PV _(0-300) ) is Y, X is
0.5 or more, preferably 0.6 to 0.8,
Y is 0.4 or less, preferably 0.3 or less. Here, PV _(nm) means a pore volume occupied by pores having a pore diameter of _{nm to} mÅ. For example, PV
_(30-100) is the pore volume occupied by pores having a pore diameter of 30 to 100 °. When X is less than 0.5 or Y exceeds 0.4, the desulfurization activity and the denitrification activity decrease.

[0017] Furthermore, the hydrotreating catalyst of the present invention has a
Of pores with a diameter of 0 to 300 mm measured by elemental adsorption method
And pores with a diameter of 40 mm or more measured by the mercury intrusion method
Volume ratio, i.e.

[0018]

(Equation 4) Is 0.7 or more, preferably 0.8 or more. 0.7
If it is less than 10, the desulfurization activity and the denitrification activity decrease.

The specific surface area of the hydrotreating catalyst of the present invention is 200 m ² / g or more. Specific surface area is 200m ²
If it is less than / g, the hydrogenation active component cannot be highly dispersed and supported on the carrier, and high catalytic activity cannot be obtained.

The boria-silica-alumina carrier used in the present invention can be produced by producing a silica-alumina carrier component and then adding a water-soluble salt of a boron compound. And a silica-alumina support component can be usually manufactured as follows. That is, (1) a method in which a silica hydrate gel and an alumina hydrate gel are each prepared in advance and then mixed, and (2) a basic substance or a water-soluble aluminum compound and a water-soluble silicon compound are mixed in a homogeneous mixed solution. (3) immersing the silica hydrate gel in a solution of an aluminum compound, and then adding an appropriate amount of a basic substance or an acidic substance to convert the alumina hydrate gel to silica. (4) immersing the alumina hydrate gel in a solution of a silicon compound, and then adding an appropriate amount of a basic substance or an acidic substance to convert the silica hydrate gel to an alumina hydrate. It can be produced by, for example, a method of depositing on a gel.

A specific method for producing the boria-silica-alumina carrier used in the present invention is, for example, as follows. To the aqueous solution of the raw material aluminum compound, an acidic or alkaline aqueous solution is gradually added, and the pH of the mixed solution is adjusted to 7 to 11, preferably 8 to 10 over about 5 to about 30 minutes, to form an alumina hydrate gel. Generate. With respect to the obtained alumina hydrate gel, the precipitated alumina hydrate gel is aged at a temperature of about 70 ° C. for 0.2 to 1.5 hours while maintaining the pH at the above set value. ₂ to 40% by weight as SiO _{2 in the} fired boria-silica-alumina support
An aqueous solution of a silicon compound is added so as to contain the solution, and a mineral acid solution is added as needed to adjust the pH to a range of about 7 to 11, and kept at a temperature of about 50 to about 80 ° C for 0.2 hours or more. Then, a silica-alumina carrier component is prepared by depositing the silica hydrate gel on the alumina hydrate gel as a core to form a silica layer.

Next, the precipitate containing the silica-alumina carrier component is filtered off, washed with an ammonium carbonate solution and water to remove impurity ions in the precipitate, and a cake-like silica-alumina carrier component is prepared. To this cake, an aqueous boric acid solution is added so as to contain 0.1 to 10% by weight as B ₂ O ₃ in the fired boria-silica-alumina carrier, and after kneading, the mixture is formed into a desired shape by a molding machine. Molding.
Finally, processing such as drying and baking is performed on the molded product. Drying is performed by heating to a temperature from room temperature to about 200 ° C. in the presence or absence of oxygen.
It is carried out by heating in the presence of oxygen to a temperature in the range of about 200 to about 800C, preferably about 600 to about 700C. By preparing a boria-silica-alumina carrier under such conditions, a carrier having a controlled pore distribution can be obtained, and a bond between boria, alumina and silica can be formed well. it can.

The boria-silica-alumina carrier used in the present invention can also be produced by preparing a silica-alumina carrier prepared by controlling the pore distribution in advance and then adding a water-soluble salt of a boron compound. .

The active component (A) constituting the hydrotreating catalyst of the present invention is at least one active component selected from Group 8 elements of the periodic table. As the active ingredient (A),
Iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), rhodium (Rh), palladium (P
d), osmium (Os), iridium (Ir) or platinum (Pt). Preferably, it is cobalt, nickel, ruthenium, rhodium, palladium, iridium or platinum. These elements can be used alone or as a mixture.

The active component (B) constituting the hydrotreating catalyst of the present invention is at least one active component selected from Group 6B elements of the periodic table. Examples of the active component (B) include chromium (Cr), molybdenum (Mo), and tungsten (W). Preferably it is molybdenum or tungsten. These elements are
They can be used alone or as a mixture.

The hydrotreating catalyst of the present invention comprises the above-mentioned active component (A) and active component (B) supported on a carrier. In particular, molybdenum-cobalt, molybdenum-nickel, tungsten- Combinations such as nickel, molybdenum-cobalt-nickel, tungsten-cobalt-nickel or molybdenum-tungsten-cobalt-nickel are preferred. Further, in addition to the active component (A) and the active component (B), the hydrotreating catalyst of the present invention may be used within a range not to impair the performance of the catalyst. A group metal such as tin, germanium or lead may be added for use. These active ingredients are preferably supported as oxides and / or sulfides, which can be prepared by presulfurization of the catalyst as described below.

The amount of the active ingredient (A) to be loaded is 0.05 to 15% by weight as an oxide. Preferably 0.
1 to 10% by weight. When the supported amount is less than 0.05% by weight, sufficient desulfurization activity and denitrification activity cannot be obtained, and hydrotreating such as hydrodearomatization and hydrorefining cannot be performed. If it exceeds 15% by weight, the free metal component not bound to the carrier increases, and a group 6B metal (active component (B)) and an inactive composite oxide are formed.
There is a problem of lowering the dispersibility of the Group 6B metal and lowering the catalytic activity, so that high desulfurization activity and denitrification activity cannot be obtained, and hydrotreating such as hydrodearomatization and hydrorefining is not possible. Can not.

The loading amount of the above-mentioned active ingredient (B) is 10 to 40% by weight as an oxide. Preferably 12 to 3
0% by weight. When the supported amount is less than 10% by weight, high desulfurization activity and denitrification activity cannot be obtained because the active sites are reduced, and hydrotreating such as hydrodearomatization and hydrorefining cannot be sufficiently performed. . If the content exceeds 40% by weight, the active component cannot be highly dispersed and maintained on the carrier, and at the same time, since the cocatalyst effect on the Group VIII metal (active component (A)) is not exerted, the decrease in the active site is suppressed. Bring
Again, high desulfurization activity and denitrification activity cannot be obtained, and hydrotreating such as hydrodearomatization and hydrorefining cannot be sufficiently performed.

The method of loading the active ingredient (A) and the active ingredient (B) of the present invention on a carrier is not particularly limited, and can be loaded by a known method. For example, it can be carried as follows. Compounds such as nitrates, acetates, formates, ammonium salts, phosphates and oxides of the active ingredient (A) and the active ingredient (B) are dissolved in a solvent to prepare an impregnating solution. , An organic acid such as citric acid, tartaric acid, malic acid, acetic acid, and oxalic acid is added to the mixture.
Adjust to about 9. The impregnating solution adjusted to about PH = 9 is dropped on the carrier with stirring to impregnate the carrier.

The solvent is not particularly limited, and various solvents can be used. For example, water, aqueous ammonia, alcohols, ethers, ketones, aromatics and the like can be mentioned. Preferred are water, aqueous ammonia, acetone, methanol, n-propanol, i-propanol, n-butanol, i-butanol, hexanol, benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, etc., and particularly preferably water. It is.

The mixing ratio of the solvent and both active components in the impregnating solution and the amount of the impregnating solution impregnated into the carrier are not particularly limited, but the ease of the subsequent impregnation operation and drying and firing operation is taken into consideration. Then, the amount of both active components carried on the fired catalyst can be selected so as to be a desired value.

The method of supporting the active ingredient is as described above, but in more detail, the carrier is immersed in a solution of a soluble salt of the active ingredient and the impregnation method of introducing the active ingredient into the carrier, or In producing the carrier, a coprecipitation method in which the active ingredient is precipitated at the same time can be adopted, and any other method may be used, but it is easy to operate and is convenient for maintaining stable catalyst physical properties. It is preferable to use a simple impregnation method.

In the impregnation operation, the carrier is immersed in the impregnating solution at room temperature or at room temperature or higher, and is maintained under the condition that the desired active ingredient is sufficiently impregnated in the carrier. The amount and temperature of the impregnating solution can be appropriately set so that a desired amount of the active ingredient is supported. Also, the amount of the carrier immersed in the impregnation solution can be determined by the desired amount of the active ingredient to be carried. Further, if desired, a third active ingredient composed of a metal of Group 4 and Group 7 of the periodic table as described above can be added.

The impregnation of the carrier with two or more active ingredients may be
(1) Two or more active ingredients are preliminarily mixed and impregnated simultaneously from the mixed solution (one-component impregnation method), and (2) Solutions of two or more active ingredients are separately prepared and sequentially impregnated ( Any method of the two-component impregnation method) can be arbitrarily adopted, but the catalyst for hydrotreating of the present invention is obtained by first supporting the active component (A) on the above-mentioned boria-silica-alumina carrier. (1st step), Then, it can manufacture by carrying an active ingredient (B) (2nd step).

Finally, the carrier impregnated with the active ingredient is molded by punching, extrusion, tumbling granulation, etc.
It is dried by a method such as air drying, hot air drying, heat drying, freeze drying and the like, and is further fired. Baking, temperature 400-700 ° C
For 1 to 5 hours. If the calcination temperature is too high, the crystals of the oxide of the supported active component are precipitated, and the surface area and pore volume are reduced, causing a decrease in the activity as a catalyst. Since the contained ammonia and acetate ions are not desorbed and the active sites on the catalyst surface are not sufficiently exposed, the activity is also lowered. It is desirable that the firing be performed gradually.

The hydrotreating catalyst of the present invention can be used by mixing with another hydrotreating catalyst, if desired. As the other hydrotreating catalyst, a known catalyst can be used.

(Hydrotreating Method) Next, a method for hydrotreating a hydrocarbon oil using the hydrotreating catalyst of the present invention will be described. The hydrocarbon oil to be subjected to the hydrotreating is not particularly limited, and examples thereof include an atmospheric distillate of petroleum crude oil, an atmospheric distillate residue, a vacuum distillate, a cracked gas oil fraction, and Any of the mixed oils can be used. In particular, vacuum gas oil, cracked gas oil, straight-run gas oil, and the like, in which it is difficult to simultaneously perform desulfurization and denitrification, are preferable.

A vacuum gas oil obtained by subjecting Middle Eastern crude oil to atmospheric distillation and vacuum distillation, a cracked gas oil having a boiling point of about 200 ° C. or more, obtained by pyrolyzing a residual oil with a coker or a bisbreaker, etc .; Light cycle gas oil (LCGO) and heavy cycle gas oil (HCGO).

The vacuum gas oil is a distillate having a boiling point in the range of about 370 to 610 ° C., which is obtained by vacuum distillation of atmospheric distillation residue oil, and has a considerable amount of sulfur, nitrogen and metal components. contains. Examples of the sulfur content include sulfur compounds such as 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene, and examples of the nitrogen content include basic nitrogen compounds such as pisazines, amines and amides, and pyrroles. Containing weakly basic nitrogen compounds such as
Metals include nickel, vanadium, iron, and the like. According to the hydrotreating method of the present invention, such desulfurization and denitrification of vacuum gas oil can be performed most efficiently.

The reaction conditions for the hydrotreating are not particularly limited, but can be selected depending on the type of the hydrocarbon oil, the target desulfurization rate and the denitrification rate, and the like. That is, a reaction temperature; 200 to 500 ° C., preferably 280
４２０420 ° C., reaction pressure; 1-200 kg / cm ² , hydrogen-containing gas rate; 100-270 L / L, and liquid hourly space velocity; 0.05-5.0 V / H / V, preferably 0.5
４4 V / H / V can be adopted. As the hydrogen-containing gas, a gas having a hydrogen concentration in the range of 60 to 100% can be used. The hydrotreating catalyst of the present invention can achieve a high desulfurization rate and a high denitrification rate under relatively severe reaction conditions under which the activity is deteriorated relatively quickly and particularly under a low reaction pressure.

In performing the hydrotreating of hydrocarbon oil,
The hydrotreating catalyst can be used in any form of a fixed bed, a fluidized bed, a boiling bed or a moving bed, but it is usually preferable to employ a fixed bed from the viewpoint of the apparatus or operation. In addition, two or more reaction towers can be combined to perform a hydrogenation treatment to achieve a high desulfurization rate and a high denitrification rate. In particular, when the hydrocarbon oil is a heavy oil,
It is preferred to use a multi-stage reaction tower.

Further, in the hydrotreating method of the present invention, it is preferable that the hydrotreating catalyst be preliminarily sulfurized before the hydrotreating of the hydrocarbon oil. In the pre-sulfurization, after the calcined catalyst is filled in the reaction tower, the sulfur-containing distillate is supplied to the reaction tower, and the temperature: 150 to 400 ° C., the pressure (total pressure);
-100 kg / cm ² , liquid hourly space velocity: 0.3-2.0 V
/ H / V and hydrogen containing gas rate; 50-1500 L
/ L under the reaction conditions to carry out the sulfurizing treatment of the active component, then switch the sulfur-containing distillate to hydrocarbon oil, set the operating conditions corresponding to the desulfurization and denitrification of hydrocarbon oil, Start the operation of the conversion process. As a method of the sulfurization treatment, in addition to the method described above, a method of bringing hydrogen sulfide or another sulfur compound into direct contact with a catalyst or adding the compound to an appropriate hydrocarbon oil and bringing this into contact with the catalyst is adopted. Can also.

[0043]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described based on embodiments. In addition,
The present invention is not limited at all by the following Examples. Example 1 A catalyst A having the properties shown in Table 1 was produced as follows. Heat 3 liters of pure water to 70 ° C., dissolve 205 g of sodium aluminate in this, and adjust the pH.
About 12 aqueous sodium aluminate solutions were prepared. Next, while adding the nitric acid solution to the aqueous sodium aluminate solution, the mixed solution was brought to a predetermined pH = about 15 minutes.
It was adjusted to 8.8 to 9.2. Subsequently, at 70 ° C. for 0.5
After aging for an hour, an aqueous solution containing an alumina hydrate gel precipitate was prepared.

An aqueous solution of sodium silicate prepared by dissolving 32 g of No. 3 water glass in 200 g of pure water was added to the obtained aqueous solution, and if necessary, a nitric acid solution was added to adjust the pH to about 9, and the temperature was increased to 70 ° C. For 0.5 hours. Thus, a slurry liquid containing precipitated particles in which the precipitate (gel) of silica hydrate was deposited on the surface of the precipitate (gel) of alumina hydrate was prepared. The slurry was filtered, and the filtered cake was washed with an aqueous solution of ammonium carbonate until the sodium concentration of the filtrate after filtration became 5 ppm or less.

An aqueous solution of boric acid was added to the cake so as to have a B ₂ O ₃ content of 1% by weight, and the mixture was kneaded while being dried in a kneader at 80 ° C. until the water content became moldable. It was molded into a 1.5 mmφ cylindrical pellet by a molding machine. The molded pellet was dried at 120 ° C. for 16 hours, and calcined at 700 ° C. for 3 hours to obtain a carrier.

The carrier is impregnated with an aqueous solution in which cobalt nitrate and nickel nitrate are dissolved so that the amount of CoO becomes 4% by weight and the amount of NiO becomes 1% by weight.
Dried at 20 ° C and calcined at 450 ° C. Next, MoO ₃
An aqueous solution of ammonium paramolybdate (molybdenum solution) was impregnated so that the amount was 14.8% by weight.
After drying at 0 ° C., it was calcined at 500 ° C. to obtain a catalyst A.

Using the catalyst A prepared as described above, the test oil was subjected to hydrogenation treatment, and the desulfurization activity and the denitrification activity of the catalyst A were measured. Table 1 shows the pore structure and chemical composition of Catalyst A, and the results of the hydrotreating test.

[0048]

[Table 1]

The pore volume of the hydrotreating catalyst was measured by a nitrogen adsorption method and a mercury intrusion method. The nitrogen adsorption method and the mercury intrusion method are described in H. Emmet et al., "Catalysis", Vol. 1, p. 123 (published by Reinhold Publishing Company) (1959) [PHEmmett, e
t.al. "Catalysis", Vol.1, p123 (1959) (Reinhold Publi
shing Co.)] and Catalysis Engineering Course, Vol. 4, pages 69 to 78 (published by Jinjinshokan) (Showa 39). The specific surface area of the hydrotreating catalyst was measured by a nitrogen gas adsorption method (BET).

As for the nitrogen adsorption method, various correction methods based on multi-layer adsorption have been proposed.
Law [EPBarrett, LG Joyner and PPHalenda, “J. of
Amer. Chem. Soc. ", 73 , 373 (1951)] and CI method [RWC
ranston and FAInkley, “Advances in Catalysis” I
X, 143 (1957) (New York Academic Press)]. Data relating to the pore volume in the present invention,
Calculated by the BJH method using the adsorption side of the adsorption isotherm. The mercury intrusion method uses a mercury contact angle of 130
°, surface tension was 485 dynes / cm, and all pores were measured as cylindrical.

The test oil and the hydrotreating method are as follows. (I) Test oil The test oil used was a vacuum gas oil obtained from Middle Eastern crude oil. Table 2 shows the properties of the test oil. (Ii) Hydrotreating test method In the hydrotreating test, a fixed-bed flow reactor was used.
First, a catalyst was filled in a reaction tube, and carbon disulfide (C
Pre-sulfurized oil prepared containing 3% by volume of S ₂ )
Preliminary sulfurization of the catalyst was performed by passing oil for 0 hours. Next, the test oil was allowed to flow for about 24 hours, and the product oil in a reaction equilibrium state was collected. Then, the desulfurization activity and the denitrification activity of the catalyst were obtained from the measurement results of the sulfur content and the nitrogen content in the test oil and the sulfur content and the nitrogen content in the produced oil. Table 2 shows the reaction conditions. In addition, the sulfur content and the nitrogen content (range) of the product oil obtained in the hydrotreating test using the catalysts prepared in Examples 1 to 4 and Comparative Examples 1 to 5 are shown.

[0052]

[Table 2]

(Example 2) In the same manner as in Example 1, except that the amount of the boric acid aqueous solution was adjusted so that the boria content was 3% by weight as B ₂ O _3. Thus, Catalyst B was prepared, and a test for hydrotreating the test oil was conducted. Table 1 shows the pore structure and chemical composition of Catalyst B, and the results of the hydrotreating test.

Example 3 Example 1 was the same as Example 1 except that the amount of the boric acid aqueous solution was adjusted so that the boria content was 7% by weight as B ₂ O _3. Similarly, catalyst C was prepared, and a test for hydrotreating test oil was performed. Table 1 shows the pore structure and chemical composition of Catalyst C, and the results of the hydrotreating test.

Example 4 A catalyst D was prepared in the same manner as in Example 1 except that 65 g of No. 3 water glass was dissolved in 200 g of pure water. A chemical conversion test was performed. Table 1 shows the pore structure and chemical composition of Catalyst D, and the results of the hydrotreating test.

Comparative Example 1 A catalyst E was prepared in the same manner as in Example 1 except that boric acid was not used, and a test oil hydrotreating test was conducted. Table 3 shows the pore structure and chemical composition of Catalyst E, and the results of the hydrotreating test.

[0057]

[Table 3]

Comparative Example 2 A catalyst F was prepared in the same manner as in Example 4 except that boric acid was not used, and a test oil was subjected to a hydrotreating test. Table 3 shows the pore structure and chemical composition of Catalyst F, and the results of the hydrotreating test.

Comparative Example 3 Example 1 was repeated except that the amount of the boric acid aqueous solution was adjusted so that the boria content was 15% by weight as B ₂ O _3. Similarly, Catalyst G was prepared, and a test for hydrotreating test oil was conducted. Table 3 shows the pore structure and chemical composition of Catalyst G, and the results of the hydrotreating test.

(Comparative Example 4) In Example 1, when preparing an aqueous solution containing a precipitate (gel) of alumina hydrate, the time required to adjust the pH by adding a nitric acid solution to an aqueous sodium aluminate solution was set. A catalyst H was prepared and a test oil hydrotreating test was performed in the same manner as in Example 1 except that the time was within about 2 minutes and the pH was set to 9.6 to 9.8. Table 3 shows the pore structure and chemical composition of Catalyst H, and the results of the hydrotreating test.

(Comparative Example 5) In Example 1, when preparing an aqueous solution containing a precipitate (gel) of alumina hydrate, the time required to adjust the pH by adding a nitric acid solution to an aqueous solution of sodium aluminate was reduced. Catalyst I was prepared and subjected to a hydrotreating test of a test oil in the same manner as in Example 1 except that the time was within about 1 minute and the pH was set to 10.0 to 10.4. Table 3 shows the pore structure and chemical composition of Catalyst I, and the results of the hydrotreating test.

As is clear from Tables 1 and 3, Examples 1 to 4 using catalysts A, B, C and D were comparative examples 1 to 4 using catalysts E, F, G, H and I. Compared to 5,
It showed excellent desulfurization and denitrification activities.

[0063]

As described above in detail and specifically, according to the present invention, boria is 0.1 to 1 as B ₂ O _3.
On a boria-silica-alumina support containing 0% by weight,
At least one active component (A) selected from Group VIII elements of the periodic table and at least one second active component (B) selected from Group 6B elements of the periodic table; and A hydrotreating catalyst having a specific pore structure and a method for hydrotreating a hydrocarbon oil using the hydrotreating catalyst can be provided. With such a hydrotreating catalyst, hydrocarbon oils such as vacuum gas oil and cracked gas oil can be hydrotreated with a high desulfurization rate and a high denitrification rate. It is possible to perform a high degree of processing such as hydrorefining.

Claims (2)

[Claims] 1. A carrier comprising boria, silica and alumina, on which at least one member selected from Group 8 elements of the Periodic Table.
A hydrotreating catalyst comprising at least one kind of active ingredient (A) and at least one kind of second active ingredient (B) selected from Group 6B elements of the periodic table, wherein the boria and the silica are hydrogen, wherein each B ₂ O ₃ as a 0.1 to 10% by weight and a SiO ₂ containing 2 to 40 wt%, and satisfies the following relational expression (1) to (4) in a carrier Catalyst for chemical treatment. (Equation 1) 2. Hydrotreatment of a hydrocarbon oil, wherein the hydrocarbon oil is brought into contact with hydrogen in the presence of the catalyst for hydrotreatment according to claim 1 to highly desulfurize and denitrify the hydrocarbon oil. Method.