JP2000000465A - Silica-alumina catalyst spport, hydrogenation catalyst using the same and hydrogenation method of hydrocarbon oil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrogenation catalyst excellent in inhibition resistance to hydrogen sulfide, providing a high activity in hydrogenation desulfurization of a hardly desulfurizable sulfur compound in the hydrocarbon oil and excellent also in hydrogenation denitrification activity and hydrogenation dearomatic activity and a hydrogenation method of hydrocarbon oil using the same. SOLUTION: A highly silica-containing alumina, containing >=30 wt.% silica and highly dispersed of silica, >=15% in >=-92 ppm peak area by the measurement of 29Si-NMR (79.5 MHz) and >=50% in >=-98 ppm peak area is used as the support, the hydrogenation catalyst is prepared by supporting at least one kind of a hydrogenation active metallic component thereon and the hydrogenation method is performed by allowing the sulfur-containing hydrocarbon oil to contact with hydrogen in the presence of the hydrogenation catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silica-alumina catalyst carrier, a hydrotreating catalyst using the same, and a method for hydrotreating a hydrocarbon oil.
The present invention relates to a hydrotreating catalyst using a high silica-containing alumina in which silica is highly dispersed as a carrier, and a method for hydrotreating a sulfur-containing hydrocarbon oil using the same.

[0002]

2. Description of the Related Art Conventionally, various catalysts for hydrotreating hydrocarbon oils have been proposed. Molybdenum and tungsten belonging to Group 6 of the periodic table are used with a refractory inorganic oxide such as alumina, silica, magnesia or the like as a carrier. Those supporting a hydrogenation-active metal component in combination with cobalt, nickel, etc. of Group VIII of the same table have already been used industrially, but in order to further improve desulfurization activity and denitrification activity, Development has been carried out from both sides of the hydrogenation active metal component and the carrier,
The present applicant has already studied the improvement of the desulfurization activity from the viewpoint of improving the dispersibility of the hydrogenation-active metal component. The silica-alumina having a low silica content is used as a carrier, and cobalt and / or a metal of Group VIII of the periodic table are used. Alternatively, by supporting nickel in the first step and then supporting molybdenum and / or tungsten of Group 6 metal of the periodic table in the second step, molybdenum as a main component is supported on the carrier with good dispersibility and uniformity. The resulting catalyst has been proposed as the ultimate high activity hydrotreating catalyst having excellent desulfurization activity (see Japanese Patent Application Laid-Open No. 60-225645).

[0003] Further, as for the carrier, the pore distribution of the silica-alumina carrier is controlled, and the pores are broadly distributed over both the micropores having a pore diameter of 300 mm or less and the macropores exceeding the pores, so that the desulfurization activity and the denitrification are improved. Hydrotreating catalysts having both excellent activities have been proposed.

However, in recent years, from the viewpoint of environmental protection measures, the demand for reducing the sulfur content of the gas oil fraction has become more severe,
In order to achieve this, the desulfurization of difficult-to-desulfurize sulfur compounds such as 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene present in the gas oil fraction can be performed, particularly, the desulfurization reaction in the presence of a large amount of hydrogen sulfide. The key point is whether or not promotion is possible. For this reason, it has been desired to further improve the performance so that the previously developed hydrotreating catalyst can be sufficiently applied to deep desulfurization of a gas oil fraction.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a highly sulfur-containing hydrocarbon oil having excellent resistance to reaction inhibition of hydrogen sulfide generated in large amounts in hydrodesulfurization, and hydrodesulfurization of a hardly desulfurizable sulfur compound. The present invention provides a hydrotreating catalyst which exhibits high activity and can cope with deep desulfurization of a sulfur-containing hydrocarbon oil, and a method for hydrotreating a hydrocarbon oil using the hydrotreating catalyst.

[0006]

Means for Solving the Problems Accordingly, the present inventors have:
In order to solve the above-mentioned problems, the present inventors conducted intensive studies on a carrier for a highly active hydrotreating catalyst, and found that the higher the silica-containing alumina carrier, the better the silica dispersibility, the more Bronsted acid sites. It has been found that it is possible to provide a catalyst for hydrotreating, which becomes a carrier having good resistance to hydrogen sulfide inhibition and high activity and which can easily desulfurize hardly desulfurizable sulfur compounds, and based on these findings, completed the present invention. .

That is, in the first aspect of the present invention, 30
Silica containing wt% or more - a alumina catalyst ^{support, (1) 29 Si-NMR} (79.5MH Z) -80ppm obtained by measurement, -86Ppm and -92p
pm peak area is 15% or more, and
Relates alumina catalyst support ^{- (2) 29 Si-NMR} (79.5MH Z) -80ppm obtained by measurement, -86ppm, silica area total peak -92ppm and -98ppm is characterized in that 50% or more Things.

A second aspect of the present invention is a hydrotreating catalyst comprising a silica-alumina catalyst carrier containing 30% by weight or more of silica and carrying at least one hydrogenation-active metal component. The alumina support contains 30% by weight or more of silica, and (1) ²⁹ Si-NMR (7
9.5MH _Z) -80ppm obtained by measurement, -8
The total area of the peaks at 6 ppm and -92 ppm is 15
% Or more and (2) ²⁹ Si-NMR (79.5
MH _Z) -80 ppm obtained by measurement, -86Pp
The present invention relates to a hydrotreating catalyst characterized in that the total area of peaks at m, -92 ppm and -98 ppm is 50% or more.

Further, a third aspect of the present invention is to provide a hydrocarbon oil,
A hydrotreating catalyst comprising a silica-alumina carrier carrying at least one hydrogenation active component, wherein the silica-alumina carrier contains 30% by weight or more of silica, and (1) ²⁹ Si-NMR ( 79.5MH _Z) -80ppm obtained by measurement, -86Ppm and -92p
pm peak area is 15% or more, and
^{(2) 29 Si-NMR (} 79.5MH Z) -80ppm obtained by measurement, -86Ppm, in the presence of -92ppm and area total of the peaks of -98ppm is 50% or more hydrotreating catalyst, hydrogen The present invention relates to a method for hydrotreating a hydrocarbon oil, which is brought into contact with hydrogen under hydrotreating conditions.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The silica-alumina catalyst carrier used in the hydrotreating catalyst of the present invention is a highly silica-containing alumina in which silica is highly dispersed. Its specificity is the following two incompatible properties which are incompatible with each other. It has a point.

That is, in order to realize a highly active hydrotreating catalyst, the silica content of the catalyst carrier is 30% by weight or more, particularly 40% by weight or less.
It is a high silica-containing alumina that is 80% by weight, and a high silica-containing alumina having a high silica dispersibility specified by ²⁹ Si-NMR (79.5 MHz) measurement.

According to the present invention, the silica content of the first specific point hydrotreating catalyst is determined by the amount of Brönsted acid effective in the hydrodesulfurization reaction, the hydrodenitrogenation reaction and the hydrodearomatic reaction. In order to suppress the coking accompanying excessive hydrocracking, the content is 30% by weight or more, preferably 40% by weight to 80% by weight. If the silica content is less than 30% by weight, the occurrence of Bronsted acid sites is small, while if it exceeds 80% by weight, excessive hydrocarbon decomposition occurs, resulting in a problem that a highly active catalyst cannot be obtained. .

The second characteristic point is that the silica content is 30% by weight.
As described above, in particular, silica is highly dispersed in the range of 40% by weight to 80% by weight, and silica dispersibility is determined by the distribution of silicon atoms and aluminum atoms via oxygen atoms obtained by nuclear magnetic resonance measurement. It is specified by the position form. Specifically, a silica-alumina carrier was converted to ²⁹ Si-NMR.
(79.5 MHz) The peak positions obtained by the measurement method are subjected to least squares fitting calculation using a Gaussian function curve, and the peak positions are -80 ppm, -86 ppm, and -92 pp.
m, -98 ppm, -104 ppm and -110 pp
The waveform is separated by m, silica dispersibility is set for each peak, and the peak area ratio is calculated. The peak position is determined based on the setting of the silica binding property adopted as the waveform separation condition in the ²⁹ Si-NMR measurement method in Examples described later. In addition, when this is represented by a coordination form of a silicon atom and an aluminum atom, it is represented by the following formulas (I) to (V).

[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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The alumina support with high silica content of the catalyst for hydrotreating of the present invention comprises: (i) separating the waveform at the peak position,
When the peak area ratio was calculated, it is considered that four aluminum atoms are coordinated (Si-4 (OAl)) with respect to the silicon atom via the oxygen atom as represented by the formula (I).
pm peak, three-coordinate (Si-3 (OAl)) represented by the formula (II)
A peak at -86 ppm considered to be two-coordinate (Si-2 (OAl)) represented by the formula (III)
(Hereinafter referred to as “NMR area ratio I”) is 15% or more, and (ii) the aluminum area is further added to the silicon area via an oxygen atom with respect to a silicon atom in the formula (i). The sum of the area ratios of peaks at −98 ppm considered to be one coordination (Si-1 (OAL)) represented by (IV) (hereinafter “N
MR area ratio II ". ) Is 50% or more.

When the NMR area ratio I is 15% or more and NM
If the R area ratio II does not satisfy both of 50% or more, good acid properties are not formed, and the desulfurization activity, denitrification activity, and dearomatic activity are reduced. It is necessary to satisfy at the same time.

In the silica-alumina having these characteristic values of high silica dispersibility, a large amount of bonds between silicon atoms and aluminum atoms via oxygen atoms are present, and the amount of Bronsted acid is increased. And the resistance to hydrogen sulfide inhibition, which is presumed to be expressed by the interaction with H2, can be improved. Therefore, the silica-alumina carrier of the present invention has both the first specific point and the second specific point, and provides a highly active hydrotreating catalyst.

When such a silica-alumina carrier is used as a component of a catalyst for hydrotreating a hydrocarbon oil, the specific surface area is not particularly limited, but may be 200.
Those having a m ² / g or more and a total pore volume of 0.4 ml / g or more are preferable.

Next, a method for producing a silica-alumina catalyst carrier will be described. The following method can be employed for producing high silica-containing alumina in which silica is highly dispersed as a carrier suitable for the hydrotreating catalyst of the present invention.

(1) A silicon alkoxide and an aluminum alkoxide are converted to an oxygen-containing polar compound such as 2
In a solution containing one or more of alcohols, amino alcohols, keto alcohols, diketones, ketocarboxylic acids, oxycarboxylic acids and dicarboxylic acids.
Mix at a temperature of 0 ° C. to 200 ° C., preferably 20 ° C. to 80 ° C. to form a homogeneous solution, and then add water at the same temperature to hydrolyze and gel the entire uniform sol.
After drying at a temperature of 200 ° C., heat treatment is performed at 200 ° C. to 1000 ° C. to disperse the polar compound remaining in the gel, whereby silica-alumina can be produced. As the heat treatment method, heat treatment using only steam or heat treatment in oxygen or air can be performed, and any of these methods can be arbitrarily selected.

In the above-mentioned production method, the silicon alkoxide and the aluminum alkoxide are respectively
Those having an alkoxyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, are suitable. Specifically, tetramethoxysilane (Si (OCH ₃ ) ₄ ), tetraethoxysilane (Si (OC ₂ H ₅ )
_4), tetraisopropoxysilane _{((Si (i-OC 3} H 7) 3), tetra tertiary - butoxysilane _{(Si (i-OC 4 H} 9) 3) silicon alkoxides such as aluminum methoxide (Al ( OC
H _{3) 3),} aluminum ethoxide _{(Al (OC 2 H 5)} 3), aluminum isopropoxide _{(Al (i-OC 3 H} 7) 3), aluminum butoxide (Al (OC ₄ H _{9) 3,} etc. Aluminum alkoxides can be used, and their concentrations can be arbitrarily selected, but the mixing ratio of silicon alkoxide and aluminum alkoxide is adjusted so that the silica in the silica-alumina carrier is 30% by weight or more. The polar compound is used in a molar ratio of 0.1 to 2 with respect to silicon alkoxide and aluminum alkoxide.
0, preferably used in a ratio of 0.1 to 15. The amount of water used for hydrolysis during gelation is suitably 0.5 to 50, preferably 1 to 40 in molar ratio to silicon alkoxide and aluminum alkoxide. In the hydrolysis, a soluble hydrolysis accelerator such as an inorganic acid, an organic acid, an inorganic alkali, or an organic alkali, particularly, a carboxylic acid (formic acid, oxalic acid, etc.), an organic acid, an amine, or an organic alkali such as an amino alcohol is used. You can also.

(2) Next, a method using a metal alkoxide in the same manner as described above, but not using an oxygen-containing polar compound, can be roughly classified into the following three methods. First, as a first method, an aluminum alkoxide is added to water and then the temperature is raised to form a cloudy sol. A mineral acid such as nitric acid or hydrochloric acid is added to the cloudy sol, and the pH of the solution after the addition is adjusted to the acid side, preferably 2 to 3, to obtain a clear sol. The silica in the silica-alumina is 3
A silica-alumina gel is prepared by adding silicon alkoxide or another silicon compound, for example, silicon halide or the like so as to be 0% by weight or more and gelling. The obtained silica-alumina gel is dried and then calcined to obtain a silica-alumina carrier. The method and conditions for drying and firing can be the same as those in the above (1). As a second method, the order of addition of the reactants is reversed with respect to the method of the preceding paragraph, a silicon alkoxide is added to water,
After the clear sol is prepared, an aluminum compound, for example, aluminum alkoxide, aluminum sulfate, aluminum nitrate, aluminum hydroxide, or the like is added to the clear sol and gelled. After gelation, silica-alumina can be obtained through drying and firing in the same manner as described above. Further, the third method is a method using a composite alkoxide, in which aluminum alkoxide is taken in cyclohexane, and trimethylsilyl acetate (CH ₃ COOSi (CH ₃ ) ₃ ) mixed with cyclohexane is refluxed while dropping, and silicon is added. Preparing an aluminum complex alkoxide; Water is added to the obtained silicon-aluminum composite alkoxide, hydrolyzed, gelled, dried and calcined by a conventional method to obtain silica-alumina.

(3) The silica-alumina carrier of the present invention can also be produced by a coprecipitation method. According to the coprecipitation method, for example, a third water glass and sodium aluminate are used as a silica source and an alumina source, respectively, and the water glass and the sodium aluminate are adjusted while adjusting the pH of an aqueous solution of a mineral acid (eg, an aqueous solution of nitric acid) to pH8. Or a water glass solution, a sodium aluminate solution and a nitric acid solution are simultaneously added dropwise to water. The amount of the silica source used is adjusted so that the silica content is 30% by weight or more based on the total weight of the silica-alumina carrier.

The alkali metal silicate as a silica source has a soluble salt of about 0.1 mol to 10 mol, preferably about 0.3 to 5 mol as an aqueous solution. About 0.1 mol
It can be used in a range of 4 moles, preferably about 0.3 mole to 2 moles.

(4) Further, a deposition method of depositing silica gel on alumina gel can be adopted. As the alumina source, a water-soluble acidic aluminum compound or a water-soluble alkaline aluminum compound, specifically, aluminum sulfate, chloride, nitrate, sodium aluminate, and aluminum alkoxide can be used. As the silica source, a water-soluble silicon compound, specifically, an alkali metal silicate (Na2O: SiO2 = 1: 2 to 1: 4)
(For example, No. 3 water glass), tetraalkoxysilane, orthosilicate, and the like can be used. These aluminum and silicon compounds are used as an aqueous solution, and the respective concentrations may be appropriately determined. The concentration of the aluminum compound is from about 0.1 mol to about 4 mol, and the silica is 30% by weight based on the total weight of the carrier. The concentration of the silicon compound is adjusted so as to be as described above.

The following is an example of a method for producing silica-alumina by a deposition method. Pure water is heated to about 40 ° C. to 90 ° C., and sodium aluminate is dissolved therein to adjust the pH to about 1
Adjust to 0-12 and keep at the same temperature. Add nitric acid solution and p
H is adjusted to 8.5 to 9.5 and aged at the same temperature for 1 to 3 hours to precipitate alumina hydrate.

Next, an aqueous solution of sodium silicate (No. 3 water glass) is slowly added to the alumina hydrate so as to be 30% by weight or more based on the total weight of the silica-alumina. Set in the range of 10, about 50 ℃ ~
Aging at a temperature of about 90 ° C. for 1 to 3 hours to deposit silica hydrate on alumina hydrate. After this treatment, the precipitate is separated from the aqueous solution by filtration, washed with an ammonium carbonate solution and water, dried and calcined to obtain silica-alumina having silica deposited on alumina formed as a core. Drying is performed at room temperature to about 200 ° C in the presence or absence of oxygen, and calcination is performed by heating to about 200 ° C to about 800 ° C in the presence of oxygen.

(5) A high silica-containing alumina carrier in which silica is highly dispersed can be produced by vapor-depositing silicon alkoxide on an alumina carrier produced by a usual method. Conversely, it can be similarly produced by vapor-depositing an aluminum alkoxide on a silica carrier.

Next, the hydrotreating catalyst of the present invention will be described. The hydrotreating catalyst is obtained by using a high-silica-containing alumina in which silica is highly dispersed as a carrier and carrying at least one hydrogenation-active metal component on the carrier.

As the hydrogenation active metal component, Periodic Table 6
One or more metals selected from the group consisting of group metals and metals belonging to group VIII of the same table can be mentioned. That is, one or more selected from the group consisting of Group 6 chromium, molybdenum and tungsten, Group 8 iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum and the like. Can be.

For hydrodesulfurization, hydrodenitrogenation and the like of sulfur-containing hydrocarbon oils, particularly, Group 6 metals and Group 8
A combination with a Group 6 metal is preferable. For example, one or more selected from the group consisting of Group 6 metals chromium, molybdenum and tungsten and a Group 8 metal such as iron, cobalt, nickel, ruthenium, rhodium, palladium and osmium , Iridium and platinum can be used alone or in combination of two or more. Specifically, it is preferable to use a combination of molybdenum-cobalt, molybdenum-nickel, tungsten-nickel, tungsten-nickel, molybdenum-cobalt-nickel, tungsten-cobalt-nickel, or the like.

Further, these hydrogenation-active metal components include metals of Group 7 of the periodic table, such as manganese, metals of Group 12, such as zinc, and metals of Group 14 (Group IVB), such as, for example,
Tin, germanium and the like can be added. In addition, these hydrogenation-active metal components are converted to oxides and / or
Alternatively, it is preferable to carry the compound as a sulfide.

The loading amount of the hydrogenation active metal component is about 0.05 to 20% by weight, preferably 0.1 to 0.2% by weight, based on the total weight of the catalyst, of the Group 8 metal as an oxide.
1 wt% to 15 wt%, Group 6 metal is about 5 wt% to 4 wt%
0% by weight, preferably in the range of 8% by weight to 30% by weight. If the Group 8 metal component is less than 0.05% by weight, the metal component relating to the interaction with the B acid is insufficient, and the hydrogen sulfide inhibition resistance is reduced, while if it exceeds 20% by weight, the dispersibility of the metal component is reduced. As the active point decreases, the catalytic activity such as desulfurization activity and denitrification activity decreases. When the content of the Group 6 metal component is less than 5% by weight, the active point decreases. On the other hand, when the content exceeds 40% by weight, the dispersibility of the metal component decreases and the desulfurization / denitrification activity decreases.

As a method for supporting the hydrogenation-active metal component, a conventionally known method can be arbitrarily selected. The carrier is immersed in an aqueous solution of a soluble salt of the active metal component to convert the metal component onto the carrier. It is preferable to employ an impregnation method to be introduced. In the impregnation operation, the carrier is immersed in the impregnation solution at room temperature or at room temperature or higher, and the conditions are maintained such that the carrier is sufficiently impregnated with the desired component. The amount and temperature of the impregnating solution can be appropriately adjusted so that a desired amount of metal is supported.

In the hydrotreating catalyst of the present invention, the order of loading is not limited even when two or more active metal components are used as described above. , A Group 8 metal component may be supported in the second step, and in the first step,
Although the Group 6 metal component can be supported and then the Group 6 metal component can be supported in the second step, in particular, after the carrier is immersed in aqueous ammonia in the first step, the Group 8 metal component is supported. It is preferable to carry out drying and firing, and then to carry the Group 6 metal component in the second step from the viewpoint of ensuring high desulfurization activity. The function of the highly dispersed and high silica-containing alumina carrier can be sufficiently exhibited by any of the methods. The carrier supporting the hydrogenation active metal component by the impregnation method, after the completion of the impregnation operation, after separating from the impregnation solution,
Washing, drying and baking can be performed by a conventional method.

The hydrotreating catalyst obtained as described above contains 30% by weight or more of silica, preferably 40% by weight to 80% by weight, and contains ²⁹ Si-NMR (54.5 HM).
z) A catalyst comprising at least one hydrogenation-active metal component supported on a silica-alumina catalyst carrier specified by the measurement, having excellent resistance to hydrogen sulfide inhibition, and having high activity in desulfurization and denitrification reactions; Therefore, it has a remarkable effect in hydrodesulfurization of sulfur-containing hydrocarbon oils, particularly gas oil fractions.

The hydrotreating catalyst of the present invention preferably has a specific surface area of about 200 m ² / g or more and a total pore volume of 0.4 ml / g or more. Cylindrical, granular, tablet-like and other irregular shapes, and any other shapes may be used. Such a shape can be obtained by a molding method such as extrusion molding, granulation molding, and the size of the molded product is 0.5 mm to 3 mm. Is preferred.

Next, a method for hydrotreating a sulfur-containing hydrocarbon oil by using the hydrotreating catalyst of the present invention will be described.

The hydrotreating method of the present invention includes all reactions caused by the contact between hydrocarbon oil and hydrogen under hydrotreating conditions in the presence of the hydrotreating catalyst of the present invention. Specific examples include hydrodesulfurization, hydrodenitrogenation, hydrodearomatization and the like, as well as isomerization and alkylation. In this case, the hydrotreating conditions can be arbitrarily selected based on the type of the feedstock oil and the desired reaction. In the hydrotreating method of the present invention, the hydrocarbon oil is not particularly limited,
Various distillate oils and residual oils may be used.
Vacuum distilled gas oil, catalytic cracked gas oil, pyrolyzed gas oil, heavy cracked gas oil, and the like can be used. Vacuum-distilled gas oil is a distillate containing a fraction having a boiling point in the range of about 370 ° C. to 610 ° C. obtained by vacuum distillation of atmospheric distillation residual oil, and has a considerable amount of sulfur, nitrogen and metal components. It contains.
For example, in the case of Middle Eastern crude oil, the sulfur content is about 2% to 4% by weight, and the nitrogen content is about 0.05% by weight.
Contains 0.2% by weight. Heavy cracked gas oil is cracked oil having a boiling point of about 200 ° C. or higher obtained by thermal cracking of residual oil and contains a considerable amount of sulfur and nitrogen.

In carrying out the hydrotreating of the sulfur-containing hydrocarbon oil, the reaction conditions can be appropriately selected according to the kind of the raw material oil, the desired desulfurization rate and the desired denitrification rate, and the reaction temperature is about 200. ℃ -500 ℃, reaction pressure; about 5-200k
g / cm ² , ratio of hydrogen gas to feed oil; about 50 to 4000
Conditions of liter / liter and liquid hourly space velocity (LHSV); about 0.05 hr ^{-1 to} 20 hr ^-1 can be employed. The hydrogen concentration in the hydrogen containing gas may range from about 60-100%.

As a method for hydrotreating a sulfur-containing hydrocarbon oil,
Specifically, deep desulfurization of a sulfur-containing gas oil fraction can also be performed effectively, without requiring particularly severe reaction conditions.
Normal desulfurization conditions, e.g., a temperature between 280C and 400C,
10kg / cm ² ~60kg / cm ² of hydrogen pressure, 1h
A liquid hourly space velocity of r ^{-1 to} 15 hr ^-1 and a hydrogen / feed oil ratio of 50 l / l to 1000 l / l can be employed. Under these reaction conditions, even non-desulfurizable sulfur compounds such as 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene can be removed.

In carrying out the hydrotreating, the hydrotreating catalyst of the present invention can be used in any form of a fixed bed, a fluidized bed or a moving bed. It is preferable to employ it. Further, depending on the type of the feedstock oil and the desired desulfurization rate, etc., the multi-stage hydrogenation treatment can be performed using two or more reaction towers.

Further, in the hydrotreating method of the present invention, the hydrotreating catalyst may be subjected to preliminary sulfurization by bringing it into contact with a sulfur-containing distillate or a distillate containing hydrogen sulfide, disulfide carbon and the like. preferable. Presulfurization is usually carried out in a reaction tower at a temperature of about 150 ° C. to 400 ° C., a pressure (total pressure) of about 2 ° C.
^{0kg / cm 2 ~100kg / cm 2} , a liquid hourly space velocity: about 0.3hr ^-1 ~2.0hr ^-1 and about 50 liters / liter to 1500 liters / liter of hydrogen-containing gas /
Processing conditions such as the distillate ratio can be employed.

[0049]

EXAMPLES The present invention will be described more specifically with reference to examples and the like. However, the present invention is not limited by the following examples and the like.

Example 1 (Catalyst I) 2-methylpentane-2,4-diol (CH ₃
Aluminum sec. In 800 ml of CH (OH) CH ₂ C (CH ₃ ) ₂ OH)
96.51 g of -butoxide (Al (O-secC ₄ H ₉ ) ₃ ) was added, and the mixture was reacted at 80 ° C. for 5 hours with stirring. Then, tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ) 69. 3 g was added, and the mixture was reacted at 80 ° C. for 12 hours with stirring to obtain a homogeneous solution. To the reaction product, 225.8 ml of water was added dropwise at a rate of 1 ml / min and hydrolyzed at 80 ° C. After completion of the reaction, the formed gel was decomposed, dried at 90 ° C., and further calcined in an air stream at 600 ° C. for 5 hours to obtain a silica-alumina catalyst carrier. The silica content in the obtained catalyst support was 50% by weight. The silica dispersibility of this silica-alumina catalyst carrier was evaluated by ²⁹ Si-NMR measurement under the following measurement conditions, and the following results were obtained.

[0051] NMR peak area ratio I 46.2% NMR peak area ratio II 80.2% The above results, the ²⁹ Si-NMR (79.5MH _Z) measurement, silica - measuring the alumina catalyst support, the resulting The peaks were determined by least squares fit calculation using a Gaussian function curve, and the peak positions were: -80, -86, -92, -98, -10
4 and -110 ppm, and the peak area ratio was calculated. The NMR peak area ratio I was -80 ppm, -86 p
pm and -92 ppm show the total area ratio of each peak, and NMR peak area ratio II is -80 ppm, -86 p
The total area ratio of each peak at pm, -92 ppm and -98 ppm is shown.

Next, nickel nitrate (Ni (NO ₃ ) ₂ .6H ₂ O) 7.
79g ammonium molybdate _{((NH 4) 6 Mo 7} O 24 · 4H
₂ O) and 9.81g, and 4.33g of citric acid are dissolved in a mixture 56.2g of concentrated aqueous ammonia and deionized water. The ratio of concentrated aqueous ammonia to pure in the mixture was adjusted so that pH = 9 with all the solutes dissolved. The impregnating solution was co-impregnated with the above-mentioned silica-alumina catalyst carrier by a pore filling method, and further dried at a temperature of 110 ° C. for 48 hours to form a disk.
It was calcined in an air stream at a temperature of 500 ° C. for 3 hours to obtain a hydrotreating catalyst I.

Example 2 (Catalyst II) The aluminum alkoxide was aluminum triisopropoxide (Al (O-iC ₃ H ₇ ) ₃ ), so that the silica content in the silica-alumina catalyst carrier was 40% by weight. After preparing a silica-alumina catalyst carrier in the same manner as in Example 1 except for the adjustment, a nickel component and a molybdenum component were supported to prepare a hydrotreating catalyst II. NMR peak area ratio of silica-alumina support
I was 71.3%, NMR peak area ratio II was 93.2, and the amount of Bronsted acid was 100 μmol / g.

Example 3 (Catalyst III) Except that the blending amount of aluminum triisopropoxide and tetraethoxysilane was adjusted such that the silica content in the silica-alumina catalyst carrier was 60% by weight, After preparing a silica-alumina catalyst carrier in the same manner as in 2, the nickel component and the molybdenum component were supported, and a hydrotreating catalyst III was prepared.

Example 4 (Catalyst IV) Except that the blending amount of aluminum triisopropoxide and tetraethoxysilane was adjusted so that the silica content in the silica-alumina catalyst carrier was 75% by weight, After preparing a silica-alumina catalyst carrier in the same manner as in 2, the nickel component and the molybdenum component were supported, and a hydrotreating catalyst IV was prepared.

Example 5 (Catalyst V) A silica-alumina support was prepared in the same manner as in Example 1 so that the silica content was 50% by weight. Was immersed in ammonia water for 2 to 10 days, filtered, washed, and dried at room temperature for 24 hours. Then, it was immersed in a 0.5N nickel nitrate aqueous solution for 2 to 10 days, filtered, washed, dried at a temperature of 110 ° C. for 24 hours, and calcined in an air stream at a temperature of 500 ° C. for 3 hours. Next, the molybdenum component was used in Example 1.
After impregnating the above nickel-supported silica-alumina by the pore filling method in the same manner as described above, drying, molding and calcining were performed to obtain a hydrotreating catalyst V.

Comparative Example 1 (Comparative Catalyst A) NiO (1.2% by weight) -CoO using silica-alumina having a silica content of 11% by weight as a carrier
(5.0 wt%) - was prepared MoO ₃ (20.0 wt%) based hydrotreating catalyst. NMR peak area ratio of silica-alumina carrier used for this catalyst I 87.7%, NM
The R peak area ratio II was 96.2%, and the amount of Bronsted acid was 25 μmol / g.

Comparative Example 2 (Comparative Catalyst B) A nickel component and a molybdenum component were carried in the same manner as in Example 1 on a commercially available silica-alumina having a silica content of 56% by weight as a carrier. NMR peak area ratio I 12.8%, NMR peak area II 32.8%
And the amount of Bronsted acid was 32 μmol / g.

Comparative Example 3 (Comparative Catalyst C) A comparative catalyst C was prepared by supporting a molybdenum component and a nickel component on a commercially available silica-alumina catalyst carrier having a silica content of 60% by weight in the same manner as in Example 1. As a result of ²⁹ Si-NMR measurement of the silica-alumina catalyst support, N
The MR area ratio I was 12% and the HMR area ratio II was 55%.

Comparative Example 4 (Comparative Catalyst D) A comparative catalyst C was prepared by supporting a molybdenum component and a nickel component on a commercially available silica-alumina catalyst carrier having a silica content of 40% by weight in the same manner as in Example 1.

The properties of the silica-alumina catalyst carriers and the hydrotreating catalysts of Examples 1 to 4 and Comparative Examples 1 to 4 are summarized in Table 1.

Example 5 (Hydrogenation treatment) Catalysts I to IV for hydrotreating of Examples 1 to 4
The sample oil I shown in Table 1 was subjected to hydrotreating under the hydrotreating condition A in Table 2 by using, and the catalyst performance was evaluated by the desulfurization activity of each catalyst (HDS1 (desulfurization activity for 4,6-DMDBT)) and Table 3 shows the evaluation results for hydrogen sulfide inhibition resistance.

Comparative Example 5 (Hydrogenation treatment) Using the comparative catalysts A to D of Comparative Examples 1 to 4, the sample oil I shown in Table 1 was subjected to hydrogenation treatment under the hydrogenation treatment conditions A shown in Table 2 to obtain desulfurization. Activity (HDS1) and resistance to hydrogen sulfide inhibition were evaluated. The evaluation results are also shown in Table 3.

Example 6 (Hydrogenation treatment) Hydrotreating catalysts I to IV of Examples 1 to 4
The sample oil II shown in Table 1 was subjected to a hydrogenation treatment under the reaction conditions shown in Table 2 by using, and the relative desulfurization activity (HDS2), relative denitrification activity (HDN) and relative dearomatic activity (HD
A) was evaluated and the results of each evaluation are shown in Table 3.

Comparative Example 6 (Hydrogenation treatment) Hydrogenation treatment was performed on the sample oil II shown in Table 1 under the hydrogenation treatment conditions B in Table 2 using the comparative catalysts A to D in Comparative Examples 1 to 4. Desulfurization activity (HDS2), relative denitrification activity (HDN) and relative dearomatization activity (HD
A) was evaluated. Table 3 shows the results of each evaluation.

Preparation of Sample Oil Sample oil I and sample oil II were prepared. Sample oil I is
It was prepared by adding dimethyl disulfide (hereinafter, referred to as DMDS) to n-hexadecane (hereinafter, referred to as nC ₁₆ ) at a ratio shown in Table 1. Sample oil II mainly consists of 4, 6
-Dimethyldibenzothiophene (4,6-DMDBT)
Light gas oil containing 0.29 wt.% Of sulfur as sulfur (L
GO-T) was prepared by adding DMDS and quinoline in the proportions shown in Table 1.

The 4,6-DMDBT simulates a hardly desulfurizable sulfur compound in a hydrocarbon oil.
DMDS simulates hydrogen sulfide producing substances in hydrocarbon oil. Separately, DMD was added to n-hexadecane.
When the sample oil to which only S was added was tested under hydrotreating condition A in Table 2, it was confirmed that DMDS was almost completely thermally decomposed and all sulfur contained in DMDS was converted to hydrogen sulfide. did.

[0068]

[Table 1]

[0069]

[Table 2]

Evaluation of catalyst performance HDS 1: 4 in sample oil I under reaction condition A
6-DMDBT the desulfurization activity H ₂ S inhibition resistance: (a) 4,6-DMDBT desulfurization at the sample oil O in the 4, 6-DMDBT desulfurization activity and (b) reaction conditions B at the sample oil I in the reaction conditions A Ratio with activity ((a) / (b)) HDS 2: relative desulfurization activity in sample oil II under reaction condition B (vs. comparative catalyst A) HDN: relative denitrification activity in sample oil II under reaction condition B ( Comparative catalyst A) HDA: Relative dearomatization activity in sample oil II under reaction condition B (Comparative catalyst A)

[0071] ²⁹ Si-NMR measurement method Measurement Conditions Instrument: BRUKER Co. DSX-400 Measurement nucleus: ²⁹ Si (79.5MH _z) Measurement mode: High Power Decoupling / Magic angl
e Spinning method Excitation pulse flip angle: 30 ° to 45 ° Waiting time: 40 seconds or more Reference sample: Peak position of sodium 3- (trimethylsiline) propanesulfonate [(CH ₃ ) ₃ SiSiC ₂ H ₆ SO ₃ NA] 1.46 ppm.

Waveform Separation Method Waveform separation was performed by least-squares fit calculation using a Gaussian function curve, Si dispersion was set for each of the obtained peaks, and data processing was performed using the peak area ratio. The waveform separation conditions are shown below. Set silica binding peak position (ppm) Peak width (ppm) Si-4 (OAl)-80.00 Calculated value Si-3 (OAl)-86.00 9.00 Si-2 (OAl)-92.00 8.00 Si-1 (OAl)- 98.00 9.00 Si-O-Si -104.00 9.00 Si-O-Si -110.00 Calculated

Method for measuring the amount of Bronsted acid The amount of Bronsted acid of the silica-alumina catalyst carrier or the catalyst for hydrotreating of the present invention was measured by the following method. 0.05 g of the catalyst carrier is inserted into a glass tube and evacuated at 500 ° C. for 1 hour in a vacuum. After degassing, the mixture is heated to 200 ° C., and 2,6-dimethylpyridine (hereinafter, referred to as “2,6-DMPy”) is aerated to be adsorbed on the carrier. After adsorption, nitrogen gas was passed at 200 ° C. for about 1 hour,
Confirm that 2,6-DMPy is not contained in the exhaust gas. The carrier on which 2,6-DMPy is adsorbed is cooled to 800 ° C for 5 minutes.
2,6-DMPy was desorbed by heating at a rate of ° C./min, the desorption amount was measured by gas chromatography, mass spectrometry, conductivity titration, etc., and the desorption amount per unit weight of the carrier was B The acid amount (μmol / g) was used.

[0074]

[Table 3]

From the above Examples and Comparative Examples, the silica content and the NMR peak area ratio I and the NMR peak area ratio
The silica-alumina carrier obtained by satisfying II has a large amount of B-acid, and is combined with an active metal component consisting of one of the metals of group 6 and 8 of the periodic table to provide a highly active catalyst. It has become clear that can be realized.

[0076]

The silica-alumina catalyst carrier of the present invention comprises:
Silica is highly dispersed high silica containing alumina,
Since the amount of Bronsted acid is large and the acid strength is high, it carries at least one active metal component selected from Group 6 metals of the periodic table and at least one active metal component selected from Group 8 metals in the Periodic Table. The resulting hydrotreating catalyst has excellent resistance to hydrogen sulfide inhibition due to the interaction between the Bronsted acid and these active metal components, and can easily desulfurize hardly desulfurizable sulfur compounds.

Further, the silica-alumina catalyst carrier of the present invention is used as a catalyst carrier for hydrotreating, and in the same manner as conventional silica-alumina, a catalyst carrier for alkylation, isomerization, etc., an adsorbent, and a filler. Etc. can also be used.

 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshinobu Okayasu 1-3-1 Nishitsurugaoka, Oimachi, Iruma-gun, Saitama F-term in Tonen Research Laboratory (reference) 4G069 AA01 AA03 AA08 AA12 BA03A BA03B BA43A BB04A BB04B BC57A BC59B BC65A BC68B BC69A CC02 DA06 EA02Y EB14Y EC03Y EC07Y EC27 ED07 ED08 FA01 FA02 FA08 FB01 FB08 FB09 FB14 FB30 FB36 FB50 FB61 FB65 4G073 BA27 BA29 BA30 BA57 BA63 BB66 BD03 FC05 UA01

Claims (7)

[Claims] 1. A silica silica containing 30 wt% or more - a alumina catalyst support, (1) ²⁹ Si-NMR obtained by (79.5MH _Z) measurement -80 ppm, the peaks of -86ppm and -92ppm total area is 15% or more, and is ^{(2) 29 Si-NMR (} 79.5MH Z) -80ppm obtained by measurement, -86Ppm, -92 ppm and the total area of the peaks of -98ppm is at least 50% A silica-alumina catalyst carrier, characterized in that: 2. The silica-alumina catalyst carrier according to claim 1, wherein the silica content of the silica-alumina catalyst carrier is 40% by weight to 80% by weight. 3. The silica-alumina catalyst support having a Bronsted acid content of 50 μmol / g or more.
Or the silica-alumina catalyst carrier according to 2. 4. A hydrotreating catalyst comprising a silica-alumina catalyst carrier containing 30% by weight or more of silica and carrying at least one hydrogenation-active metal component, wherein the silica-alumina catalyst carrier comprises (1) _{^{) 29 Si-NMR (79.5MH Z}} ) -80ppm obtained by measurement, it is -86ppm and the total area of the peaks of -92ppm 15% or more, ^{and, (2) 29 Si-NMR} (79.5MH Z) A hydrotreating catalyst, wherein the total area of peaks at -80 ppm, -86 ppm, -92 ppm, and -98 ppm obtained by the measurement is 50% or more. 5. The method according to claim 5, wherein the hydrogenation-active metal component is the sixth component of the periodic table.
5. The hydrotreating catalyst according to claim 4, wherein the catalyst is at least one active component selected from the group consisting of group metals and at least one active component selected from the group consisting of metals belonging to group VIII of the same table. 6. A method for hydrotreating a hydrocarbon oil, which comprises contacting the hydrocarbon oil with hydrogen under hydrotreating conditions in the presence of the hydrotreating catalyst according to claim 4 or 5. 7. The method for hydrotreating a hydrocarbon oil according to claim 6, wherein the hydrocarbon oil is a sulfur-containing gas oil fraction.