JPS61107946A - Hydrotreating catalyst - Google Patents

Abstract

PURPOSE:To enhance a desulfurization ratio and a denitrification ratio, by forming a hydrotreating catalyst by supporting metals belonging to the Groups VI, VIII of the Periodic Table by an alumina carrier containing a specific amount of silica and having fine pores with a specific particle size. CONSTITUTION:An alumina or alumina-containing carrier, which satisfies characteristic values such that the volume of fine pores with a pore size of 0-300Angstrom occupies 80% or more by volume of all fine pores of a catalyst and the average fine pore size of the pore size of 0-300Angstrom is 30-80Angstrom while the volume of fine pores with a pore size of 300-150,000Angstrom is 0.01-0.1ml/g and a specific area is 200-400m<2> and about 2-40wt% of silica is contained, is formed. One or more of a metal selected metals belonging to the Groups VI of the Periodic Table and one or more of a metal selected from metals belonging to the Group VIII are supported by this carrier to prepare a hydrotreating catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a catalyst used in the hydrotreating of hydrocarbon oils, and in particular to a specific catalyst comprising a carrier supporting a hydrogenation active component. The present invention relates to a hydrotreating catalyst having a pore distribution.

BACKGROUND OF THE INVENTION In the description of the present invention, "hydrotreatment" refers to a treatment method by contacting hydrocarbon oil with hydrogen.

Hydrorefining with relatively less severe reaction conditions, and hydrorefining with relatively more severe reaction conditions that involve some decomposition reactions.

Hydrogen isomerization. It includes hydrodealkylation and other reactions of hydrocarbon oils in the presence of hydrogen.

Examples include hydrodesulfurization, hydrodenitrogenation, and hydrocracking of distillate oils and residual oils of atmospheric distillation or vacuum distillation;
This includes hydrorefining of lubricating oil fractions, etc. 1
Since the catalyst of the present invention is particularly effective in hydrodesulfurizing distillate oil or residual oil of atmospheric distillation, and mixed oils thereof, the present invention will be mainly described below.

The desulfurization method by hydrorefining of sulfur-containing hydrocarbon oil using a catalyst containing a hydrogenation active component has been known for a long time, but it has been used industrially to desulfurize heavy hydrocarbon oil containing asphalt and metal-containing compounds. The establishment and improvement of the hydrodesulfurization method, which is capable of reducing pollution, is currently in great demand as a non-polluting process.

Heavy hydrocarbon oil containing heavy substances obtained as a residue from the distillation of crude oil at normal pressure or reduced pressure is important as a fuel for power and heating in all kinds of industrial equipment, including power generation equipment, and as fuel for Daisei ships. However, compared to light distillate oil, it has a higher sulfur content, and when burned in a lock heating furnace, etc., it produces sulfur dioxide gas and sulfuric anhydride, which are released into the atmosphere along with exhaust gas. hand.

It causes air pollution and causes pollution problems. In addition, residual oil contains nitrogen compounds as well as sulfur compounds, which generate nitrogen oxides (NOX (X is mainly 1 or 2)) when burned, which also causes air pollution such as photochemical smog. It shapes possibilities.

Sulfur compounds and nitrogen compounds in hydrocarbon oil.

each by a hydrogenation reaction in the presence of a catalyst.

If separated from hydrocarbon oil as hydrogen sulfide and ammonia, etc.
I can do that.

However, heavy hydrocarbon oils, especially residual oils, contain catalyst contaminants, such as vanadium and organic compounds of iron and other metals, which rapidly degrade the activity of the catalyst and prevent its regeneration. inhibit.

Furthermore, the residual oil contains asphaltone or a polycyclic aromatic polymer compound such as asphalt.

In hydrodesulfurization and hydrodenitrogenation, this substance adheres to the catalyst surface and causes the formation of carbonaceous deposits, clogging the pores of the catalyst and deteriorating its activity. To implement this, extremely difficult technical challenges are encountered.

Conventionally, various studies have been made on catalysts used for hydrodesulfurization of residual oil. For example, in order to perform hydrodesulfurization and hydrodenitrogenation of hydrocarbon oils containing asphalt and metal-containing compounds, the pore distribution of the hydrotreating catalyst used greatly affects its activity and ability to maintain activity. In anticipation of this, in order to prevent the infiltration of asphalt and metal-containing compounds in the feedstock oil, we used a catalyst with a pore distribution in which the pore volume with a pore radius of 80 A or more was reduced by 10% of the total pore volume. The method used (% Publication No. 45-38142) or in the hydrodesulfurization of the same residual oil with a radius of 12
A method using a catalyst in which the volume of pores of 0A or less is distributed relatively uniformly at intervals of 1OA (Japanese Patent Publication No. 38143/1983) is known. Also, at least 50 of the total pore volume of the particles having a pore size χ in the range of about 5O-10OA
A hydrodesulfurization catalyst for crude oil or prefixed crude oil having a pore volume of up to 25 mm and a pore size in the range of 0-5 OA has also been disclosed (Japanese Patent Laid-Open Publication No. 10356/1983).

Problems to be Solved by the Invention The inventors of the present invention also recognized that the pore distribution of a catalyst has an important effect on catalyst performance, and conducted numerous studies. In the course of this research, the present inventors.

When carrying out hydrodesulfurization of not only residual oils containing asphalt as mentioned above but also distillate oils from atmospheric distillation or vacuum distillation, it is necessary to use hydrogenation-active metals to obtain excellent catalyst performance (activity and ability to maintain activity). It has been found that it is extremely important to limit the pore distribution of the supported catalyst within a specific range.

In the conventional hydrodesulfurization method as described above, the pore distribution of so-called macropores with a pore radius of 300 mm or more in the catalyst used has not been sufficiently studied, and its influence on catalyst performance has been ignored. There is. That is, the conventionally disclosed technology is as follows.

The focus is on so-called micropores, but macropores alone contain large amounts of sulfur, nitrogen, metals, asphalt, and other impurities, such as atmospheric distillation residue oil, vacuum distillation gas oil, vacuum distillation residue oil, etc. It is not possible to improve the activity and ability to maintain activity in hydrorefining hydrocarbon oil.

SUMMARY OF THE INVENTION The inventors have discovered that the pore distribution over the inner regions of the micropores and macropores of the catalyst has a profound effect on desulfurization and denitrification. That is.

The volume of pores with a diameter in the range of 0 to 300 A measured by nitrogen adsorption method is 80% or more, preferably 90% or more of the total pore volume of the catalyst, and the average pore volume in the diameter range of 0 to 300 A is The pore diameter is 30-80A, preferably 40-70A.

Furthermore, the pore diameter measured by mercury intrusion method is 300 to 150.
,000 Å with a pore volume of 0.01 to 0.1 ml
/ g - preferably 0.02-0.08 m// g
It has been found that a catalyst having a specific surface area of 200 to 400 m"/g, preferably 250 to 35 m"/g, exhibits a very remarkable desulfurization effect. In other words, upon contact with hydrogen in the presence of a hydrorefining catalyst, heavy hydrocarbon oil, especially asphalt and resin contained in residual oil, enter the pores of the catalyst, causing deterioration of catalyst activity. What is the pore volume of macropores to prevent this? It is necessary to reduce the

It has become clear from various studies that the pore volume distribution has an important influence on the activity of the catalyst and especially on improving the ability to maintain the activity. That is, the pore volume at a diameter of 0 to 300 A is 80% or more of the total pore volume.

The catalyst, which preferably accounts for 90% or more, does not cause pore clogging due to carbonaceous adhesion or metal adhesion due to contact with asphaltone or an organometallic compound, and has an excellent ability to maintain activity.

0.01 to 0 pores in the range of 300 to 150,0 OOA
．． 1mA/g, preferably 0.02-0.08
Controlling m//glc is also extremely effective in preventing secondary pore clogging by macromolecules.

A carrier containing 2 to 40% by weight of silica has excellent solid acidity and solid acidity distribution.

It has activity in cutting carbon-sulfur and carbon-nitrogen bonds. In particular, its excellent solid acidity makes it more suitable for carbon-nitrogen bond cleavage, resulting in unexpectedly better results than other bottom-based catalysts. Naturally, the carbon-sulfur bond cleavage activity is also improved by adding a metal hydrogenation component, and as a result, it has excellent selectivity in desulfurization and denitrification activities.

Furthermore, it has been found that the silica-alumina support can effectively disperse silica, alumina, and active metal components as well. Namely.

In addition to the general immersion support, dispersion support due to the interaction between the solid acidic points generated in the aluminum element and the metal component, and a type of ion exchange through a single reaction are also possible. This dispersed support is formed by ionic bonding between group 1 and alumina.
It is also effective for the method of carrying family members.

The present invention was completed by elucidating the effect of the pore distribution over the inner regions of the micropores and macropores of the catalyst on desulfurization and denitrification as well as the effect of silica in the support.

To summarize the present invention: 1. The present invention provides a method for dispersing silica on an alumina or alumina-containing support containing about 2 to 40 weight molecules of silica and one or more metals selected from the group of Group VIB metals of the periodic table. A catalyst for hydrotreating comprising one or more metals selected from the group of metals of Group 1 of the Periodic Table of Elements.

(2) The volume of pores having a diameter in the range of 0 to 300 A is at least 80% of the total pore volume of the catalyst, preferably at least 90 A.

■ Average pores within a diameter range of 0 to 300 A ■ Pore volume within a diameter range of 300 to 150,000 Å is 0.01 to 0.1 ml 17 g, preferably 0°02
~0.08 mA/g.

(2) Specific surface area of 200 to 400 rn"/g, preferably 250 to 350 m"/g.

The present invention provides a hydrotreating catalyst.

Next, to explain the carrier in more detail, alumina,
It is already known that solid acids such as silica, alumina-silica, and magnesia are catalyst components that reach the desulfurization and denitrification reactions of hydrocarbon oil. It is important to maintain the retention, and for this purpose acidity control can be achieved by controlling the silica content. The present inventors have determined the catalytic ability and selectivity of the hydrogenation reaction of hydrocarbon oil by adjusting the cracking activity based on acidic control based on the silica content in the carrier and determining the pore structure of the catalyst as described above. I admit that I can't adjust the stone. This type of selectivity has the effect of saving hydrogen consumption in desulfurization and denitrification of hydrocarbon oils, and preventing a decrease in catalyst activity due to the production of carbon components associated with 1-cracking reactions. play a very important role.

Therefore, in the hydrodesulfurization reaction or hydrodesulfurization reaction, as mentioned above, in order to control the increase in hydrogen consumption or the formation of coke due to excessive decomposition reaction, it is necessary to include silica in the alumina-containing carrier. The amount is about 2-40% by weight, preferably about 5-20% by weight.

More preferably, the total number should be in the range of 10 to 16 times.

The support used in the catalyst of the present invention is alumina or an alumina-containing material containing about 2 to 40% by weight of silica, as described above. The alumina-containing material is a composition obtained by blending alumina with other carrier materials. For example, one or more of magnesia, calcium oxide, zirconia, titania, boria, hafnia, crystalline zeolite, etc. are added to alumina. Can be blended. The silica is.

As mentioned above, it is suitable for controlling the solid acidity of the catalyst, so it is preferably about 2 to 40% by weight in the carrier.

It is used in a range of about 5 to 20 weight. A more preferred silica content is in the range of about 10-16% by weight. Silica provides strong acid sites to the catalyst.

While increasing the cracking activity of the catalyst, 1 e.g.

Magnesia has the effect of reducing the strong acid sites of alumina-silica and the like, and at the same time increasing the weak acid sites, thereby improving the selectivity of the catalyst. The above magnesia, calcium oxide, zirconia, titania, boria.

The amount of refractory inorganic oxides such as hafnia and crystalline zeolite is approximately 1 to 10 weight ft based on the alumina-silica.
A range of 1% is appropriate.

As alumina, r-alumina, χ-alumina or η
- Alumina or mixtures thereof are suitable, but any one that provides the pore distribution and properties disclosed in the present invention may be preferably used.

Alumina-silica can be produced by producing alumina and silica gels in advance and mixing them together, or by immersing silica gel in an aluminum compound solution, adding an appropriate amount of a basic substance, and then producing alumina gel. A method of depositing on silica gel, a method of adding a basic substance to a uniform mixed solution of a water-soluble aluminum compound and a water-soluble silicon compound, and co-precipitating both can be adopted.

In order to obtain the pore distribution and characteristic values necessary for the hydrotreating catalyst used in the present invention, the temperature in the precipitation and aging of alumina and silica hydrates is 60°C.
Conditions of 0.5 to 3 hours at ~90°C are required.

For example, water-soluble compounds 1 as specific raw materials to obtain catalysts with extra-pore fabrics and characteristic values.

Water-soluble acidic aluminum compounds or water-soluble alkaline aluminum compounds, specifically aluminum sulfates, chlorides, nitrates, alkali metal aluminates, aluminum alkoxides, and other inorganic or organic salts can be used. As the water bathable silicon compound, alkali metal silicate (NIL!0: 5iOt=1:
Silicon-containing compounds such as aL tetraalkoxysilane and orun silicate ester with a preferable ratio of 2-1:4 are suitable. These aluminum and silicon compounds can be used as an aqueous solution, and the concentration of the aqueous solution is
Although not particularly limited and may be determined as appropriate, the concentration of the aluminum compound solution is approximately 0.1-4.
．． It can be employed within the range of 0 mol.

An example of an embodiment of the method for producing an alumina-silica carrier suitable for the hydrotreating catalyst of the present invention is as follows.

Acidic aluminum aqueous solution and alkali hydroxide are added to warm water at about 50 to 98°C to adjust the pH to about 6.0 to 11.0. Preferably adjusted to a range of about 8.0 to 10.0, about 50 to 9
Bring to a temperature of 8°C and hold for at least 1 hour. Add an aqueous solution of alkali silicate to this, and if necessary, add a mineral acid solution to adjust the pH to about 8.0 to 10.0. After this treatment is completed, the precipitate is filtered, washed with an ammonium carbonate solution and water to remove impurity ions, and subjected to treatments such as drying and combustion to form a carrier.

Drying in the presence or absence of oxygen.

It is heated to room temperature - about 200°C, and firing is carried out by heating in the range of about 200 to 800°C in the presence of oxygen.

As the hydrogenation-active metal component to be supported on the carrier, one or more metals selected from the group of group Ⅰ metals and group 1 metals of the periodic table are selected. Namely, chromium, molybdenum and tungsten of group II, iron of group II,
cobalt, nickel.

One or more selected from palladium, platinum, osmium, iridium, ruthenium, rhodium, etc. are used. For hydrodesulfurization of hydrocarbon oil, especially
Combinations of group metals and art group metals 1 For example, molybdenum-
Combinations such as cobalt, molybdenum-nickel, tungsten-nickel, molybdenum nickel, molybdenum-nickel, or tungsten-cobalt-nickel can be preferably used. These active metal components include metals from Group 1 of the Periodic Table of the Elements, such as manganese, and metals from Group 1.

For example, tin, germanium, etc. can be added.

These hydrogenation active metal components are preferably supported as oxides and/or sulfides.

As the supporting method, an impregnation method in which the carrier is immersed in a solution of a soluble salt of the metal and the metal component is introduced into the carrier, a coprecipitation method in which the metal component is simultaneously precipitated during the production of the carrier, etc. can be adopted. Although any method may be used, it is preferable to use an impregnation method in order to ensure operational aspects and physical properties of the catalyst. In the impregnation operation, the carrier is immersed in an impregnating solution at room temperature or above room temperature, and the carrier is maintained under conditions such that the desired components are sufficiently impregnated into the carrier. The amount and temperature of the impregnating solution can be adjusted as appropriate to support the desired amount of metal. The t of the carrier immersed in the impregnating solution depends on the amount of support.
Determine.

The supported amount of the metal component may be in the range of about 1 to 10% by weight for the νth mass group metal as an oxide, based on the catalyst, and in the range of about 5 to 30% by weight for the group I metal.

Depending on the type of supported metal, either one-component impregnation method or two-component impregnation method may be employed. In other words, in order to support two or more types of metal components, two or more types of metal components are mixed and impregnated simultaneously from the mixed solution [-liquid impregnation method], or solutions of two or more types of metal components are separately applied. It is also possible to prepare and impregnate sequentially (two-component impregnation method).
The present invention does not limit these methods in any way.

However, one of the catalysts according to the present invention uses silica alumina or a silica alumina-containing material as described above as a support, and on the support is first applied one or more metals selected from the group Vffi group metals of the periodic table of the elements. of metal (
First step) A preferred method is to support one or more metals selected from the group VIB group metals of the periodic table of elements (second step). To explain in more detail,
According to this method, the hydrogenation-active metal component supported on the carrier in the first step is one or more metals selected from the group of metals of the Group 1 of the Periodic Table of Elements. That is, the first
One or more selected from the group iron, cobalt, nickel, palladium, platinum, osmium, iridium, ruthenium, rhodium, etc. are used. Preferably cobalt and nickel will be used alone or in combination.

The hydrogenation active metal component supported on the carrier in the second step is one or more metals selected from the group VIB group metals of the periodic table. That is.

One or more selected from Group VIB chromium, molybdenum, and tungsten are used. Preferably molybdenum and tungsten may be used alone or in combination. It would also be possible to add a third metal if desired.

The hydrogenation active metal components of Group 1 and Group VIB are preferably supported as oxides and/or sulfides, and in the supporting method using the first and second steps, the amount of active metal components supported is , on a catalyst basis as an oxide, Part VII
Group metals from 1 to 10% by weight.

Preferably it is 1.5 to 8% by weight, more preferably 2 to 5% by weight, and the Group ①B metal is 5 to 30% by weight.

Preferably 8-25% by weight, more preferably 15-20%
The weight is qb. If less than 1% by weight of the Group 1 metal is supported, a sufficient catalyst cannot be obtained, and if it is more than 10% by weight, the amount of free metal components that are not bonded to the support increases. When the free component of Group 1 metal increases.

When a Group VIB metal is supported in the next step, an inert composite oxide is generated, reducing the dispersibility of the Group VIB metal,
Decrease catalyst activity. On the other hand, if the amount of Group VIB metal is less than 5 qb, no activity will be obtained, and if it is more than 30 qb, the dispersion will decrease and at the same time the promoter effect of the Group VIB metal will not be exhibited.

In the above method, the method for supporting the active metal component on the carrier in the first and second steps is as follows.

An impregnation method can be employed in which the carrier is immersed in an aqueous solution of a soluble salt of the metal to introduce the metal component into the carrier. In the impregnation operation, the carrier is immersed in an impregnating solution at room temperature or above room temperature, and the carrier is maintained under conditions such that the desired components are sufficiently impregnated into the carrier. The amount and temperature of the impregnating solution can be adjusted as appropriate to support the desired amount of metal. The amount of support to be immersed in the impregnating solution is determined depending on the amount of support.

The shape of the catalyst may be cylindrical, granular, tablet, or any other shape, and such a shape can be obtained by a molding method such as extrusion molding or granulation molding. The diameter of the molded product is 0.5-3
．． A range of 0 is preferred.

The carrier impregnated with the hydrogenation-active metal component is washed with water, dried and calcined after the impregnation solution is separated.

The drying and calcination conditions may be the same as those for the carrier.In the hydrodesulfurization of single heavy hydrocarbon oil, the catalyst is
It is preferable to carry out presulfurization prior to use. The method will be described later.

In this way, the catalyst produced is prepared on an alumina or alumina-containing support containing about 2 to 40% by weight of silica, and one or two elements selected from the group of metals of group 1 of the periodic table. With metal over the ridge.

A hydrotreating catalyst comprising one or more metals selected from all metal groups in Vll of the Periodic Table of the Elements, further comprising: The total pore volume of the catalyst is 80 inches or more.

(2) The average pore diameter within the concavity with a diameter of 0 to 300 A is 30 to 80 A.

(Diameter: 300-150.0 OL) Pore volume in range A is 0.01-0.1 m//g.

■ Specific surface area is 200-400m” 71g.

Total pore volume; 0.5 to 1.0 m
jl/g, bulk density; approximately 0.5 to 1.0 g/n1. Side breaking strength: approx. 0.8-3- Oklil/mtx
To realize a catalyst for hydrorefining hydrocarbon oil which is suitable for hydrocarbon oil.

The nitrogen adsorption method and mercury intrusion method used to measure the pore volume of catalysts are described in "Catalysis" by P. H. Emmett et al.
Volume 1, page 123 (Reinhold Publishing)
Company Publishing) (1959) P*Ha gmm
stt, et a &'catalysis' + 1
+123 (1959) (Reinhold Public
shing Co-) and Catalyst Engineering Course, Volume 4,
According to the method described on pages 69 to 78 (published by Chijinshokan) (1962).

In the mercury intrusion method, the contact angle of mercury to the catalyst Y14
0', fi surface tension is 480 dynes/cIIL.

All pores were assumed to be cylindrical.

Various correction methods have been proposed for the desired adsorption method (based on multimolecular layer adsorption, among which the BJH method (E, P,
Barrett, L.G., Jo7ner and
P-P.

Ha16Hda, JsAmsr,, Chew, 5o
cz '73e373 (1951)] and the CI method (R
e W, Cranston and F, A, I
nk16y1'Advances in Cataly
sis, 'IX, 143 (1957) (Ne
w Yark Academic Press )]
is commonly used.

Data related to pore volume ntK in the present invention is obtained by using the adsorption side of the adsorption isotherm, and using the DB method (p, Dollimorea
nd G., R. Heal, J. Appl., Ch.
Em., 14.109 (1964)).

A method for hydrodesulfurization of hydrocarbon oil by using a catalyst according to the present invention will be described.

As the heavy hydrocarbon oil, vacuum distilled gas oil 1 heavy cracked oil, etc. can be used. Vacuum distilled light oil.

Approximately 250 ° C ~ 5 obtained by vacuum distillation of normal pressure M distillation residue oil
It is a distillate oil containing a fraction having a temperature in the range of 60° C. and contains considerable amounts of sulfur, nitrogen and metals. For example, an example of vacuum distilled gas oil from Middle East crude oil contains about 2 to 4% by weight of sulfur and about 0.05 to 0.2% by weight of sulfur. Also, residual carbon content Y0.405
Contains 1 iits.

Heavy cracked oil is obtained by thermally decomposing residual oil at approximately 200°C.
For example, light oil obtained from coking and visbreaking of residual oil can be used as a cracked oil having a boiling point above 1.

Furthermore, hydrocarbon oils include those containing sulfur, nitrogen, asphalt, and metal-containing compounds, and have a boiling point of approximately 480°C or higher, and contain residual oil from normal pressure or vacuum distillation of crude oil. - For example, a residual oil having a hydrocarbon component having a boiling point of about 480 DEG C. or higher at normal pressure ranges from about 30 to 100 weights/kil.

Usually about 1 to 10% by weight sulfur, about 0.1 to 1% nitrogen, about 10 to 1,000 ppm metals, and about 1% by weight nitrogen.
Contains a heavy amount of residual carbon (Conradson).

Said hydrogenation fI! As the raw material oil for IX, the above-mentioned atmospheric distillation residue oil, vacuum distillation residue oil, vacuum distillation gas oil heavy cracked oil, atmospheric distillation gas oil, or a mixture thereof can be used.

The reaction conditions can be appropriately selected depending on the type of raw oil, desulfurization rate, denitrification rate, etc. That is, 1 reaction basicity; about 350 to 450°C, 1 reaction pressure] about 30 to 200 k
l? /i, hydrogen-containing gas rate; approximately 50 to 1,500/
//, and liquid space velocity; about 0.2 to 2.0 V/H/V is adopted. The hydrogen concentration in the hydrogen-containing gas is approximately 60 to 10
A range of 0 is fine.

The catalyst according to the present invention can achieve a high desulfurization rate even under reaction conditions with little activity deterioration and low harsh dust, especially at low reaction pressure.

In carrying out hydrodesulfurization, the catalyst can be used in any of the fixed bed, fluidized bed, or moving bed formats as described above, but it is preferable to use a fixed bed from the standpoint of equipment or operation. preferable. or.

A high desulfurization rate can also be achieved by combining two or more reaction towers to perform hydrodesulfurization.

Furthermore, the catalyst of the present invention can also be used by filling a card drum for the purpose of removing metals before a main reaction tower mainly for desulfurization and denitrification reactions.

Preferably, the catalyst is presulfided before use. Presulfurization can be carried out in situ in one reaction column. That is, calcined catalytic distillate oil, temperature: about 150-4000G, pressure (total pressure) about 12O-10
0kl? /c4. Liquid space velocity - approx. 0.3-2.0 V/
Contact in the presence of H/V and about 50-1.500 νl of hydrogen-containing gas, and after the sulfidation treatment is completed, the Kansai distillate is switched to feedstock oil, and the operating conditions are set appropriate for desulfurization of the feedstock oil, and operation is started. Start. In addition to the above methods, hydrogen sulfide or other sulfur compounds may be brought into direct contact with the catalyst, or may be added to a suitable distillate and brought into contact with the catalyst.

Examples Example 1 3.6 μm of pure water was heated to 70°C and aluminum sulfate solution (
After adding 187.5 g of aluminum sulfate and 180 g of M water, 45 g of sodium silicate (JISB water glass) was added.
, 100 g of pure water) and a sodium aluminate solution (125 g of sodium aluminate, 400 g of pure water) were added dropwise, and after adding 5 mmol of tartaric acid to the alumina, the pH was adjusted to about 9.0 with a sodium hydroxide or nitric acid aqueous solution. Then, the mixture is aged at about 70°C for about 2 hours.

The generated silica alumina gel was filtered and washed with a 1% ammonium carbonate solution to reduce the sodium concentration of the filtrate to 1 to 5 pp.
Wash until it becomes less than m.

The resulting gel was dried at 120° C., then kneaded with water, crystalline cellulose, and a polymerization aid such as acetic acid, and molded into a pellet of 1.5 fiΦ using an extrusion molding machine.

The pellet was dried at 120° C. and then fired at 600° C. for 3 hours to obtain a carrier.

The obtained carrier was immersed in ammonium molybdate salt to support about 15% of M@, and then dried and calcined. After that, it was immersed in a cobalt nitrate aqueous solution to contain about 5.0% Co.
o was used as a supported catalyst after drying and calcination.

The properties are shown in Table 1.

Comparative Example A catalyst was prepared in the same manner as in Example 1 except that the sodium silicate aqueous solution and tartaric acid were not added. The properties are shown in Table 1.

Example 2 3.6 g of pure water was heated to 70°C, and an aluminum sulfate solution (187.5 g of aluminum sulfate, 180 g of f4 water
g) After adding Y, a mixed solution of sodium silicate (28 g of JIS No. 3 water glass, 100 g of pure water) and sodium aluminate solution (125 g of sodium aluminate, 400 g of pure water) was added dropwise, and 20 mmol of glutamic acid was added. , p
Hydroxylation to Hχ9.0-9.2) Adjust with IJum or nitric acid. The temperature was then maintained at about 70°C for about 3 hours.

The gel thus obtained The subsequent steps are as follows: Example 1
A catalyst was obtained in the same manner as above. Properties are shown in Table 1.

Example 3 3.6 g of pure water was heated to 70° C. and a sodium aluminate solution (120 g of sodium aluminate) was added to it.

After adding Y (200 g of pure water) and an aluminum sulfate solution (183 g of aluminum sulfate, 400 g of pure water, 2 g of citric acid), adjust the pH to 8.8 with sodium hydroxide or nitric acid.
-9.0 and held for about 1 hour.

Add to this sodium silicate (JISa water glass 56g,
The pH was maintained at 9.2 by adding 150 g of pure water and maintained for an additional 1 hour. The gel washing, drying, and baking steps were the same as in Example 1 to obtain a carrier.

After mixing ammonium molybdate and nickel nitrate solution, loading active metal species for catalyticization.

Ammonia is added to prepare a mixed ammonium complex salt, and in one step, the amount of NiO is about 5.0, the amount of MeOs is about 5.0,
About 15% by weight was supported.

Table 1 shows the physical properties of the obtained catalyst.

Table 1 C@0 4.6 4.5 4.5NiO--
5,2- M@O814,614,915,514,6Stow
10.5 6.6 18.9 0Altos
Remaining amount Remaining amount (t Remaining amount Remaining amount 3
00- 0026 0.031
0.048 0yu12150.0
00 Semi-uniform pore diameter Effect of the invention A kerosene fraction was hydrogenated using the catalysts of Example 1 and Comparative Example. The reaction conditions are as follows.

Reaction temperature ('C) 260 Reaction pressure (k+
? /crIl) 42 Catalyst filling @ (m/) 15 Feed flow rate (
V/H/v) 2. OH2 feed ratio (S
CF/B) 1000 catalyst Example 1
Comparative example Desulfurization rate (%) 99°190 Smoke point 1 28.5 23.1 Sulfur content of raw oil 0.25Wt Smoke point
21.9+m Specific gravity 1574°C 0.8041 Aromatic 26.0 (vo1%) Using the catalysts of Example 2 and Comparative Example, atmospheric pressure gas oil fraction of Middle Eastern crude oil was used as feedstock and hydrogenated under the following reaction conditions. processed.

Reaction conditions Reaction temperature ('C) 300 Reaction pressure (k
l? /d) 20 feed flow rate (V/H/
V) t,.

H1 feed ratio (SCF/B) 1000 Catalyst loading amount 15 Catalyst Example 2 Comparative example Desulfurization rate
95.0 84.0 Denitrification rate 83.1
39.0 Raw material oil properties specific gravity 15/4°C 0.8501 Sulfur content t (vt ratio) 1.21 Nitrogen content t (ppm) 72 As understood from the above comparative test, the hydrotreating catalyst according to the present invention can have a good desulfurization rate and denitrification rate by having a specific pore distribution. That is, the catalyst according to the present invention has excellent activity and activity maintenance ability, and has the effect of effectively hydrogenating hydrocarbon oil.

Claims (1)

[Scope of Claims] 1) One or more metals selected from the group of Group VI metals of the Periodic Table of Elements, and one or more metals selected from the group of Group VI metals of the Periodic Table of Elements, on alumina or an alumina-containing support containing about 2 to 40% by weight of silica; Table VII
A hydrogenation catalyst comprising one or more metals selected from the group I metals supported, wherein (1) the volume of pores having a diameter in the range of 0 to 300 Å is 80% or more of the total pore volume; (2) the average pore diameter within the diameter range of 0 to 300 Å is 30 to 80 Å; (3) the pore volume within the diameter range of 300 to 150,000 Å is 0.01 to 0.1 ml/g; (4) a catalyst for hydrogenation treatment having a specific surface area of 200 to 400 m^2/g; 2) (1) The volume of pores having a diameter in the range of 0 to 300 Å is 90% or more of the total pore volume of the catalyst, (2) The average pore diameter within the diameter range of 0 to 300 Å is 40 to 70 Å, (3) The pore volume within the diameter range of 300 to 150,000 Å is 0.02 to 0.08 ml/g, and (4) The specific surface area is 250 to 350 m^2/g. The hydrotreating catalyst described above. 3) The hydrotreating catalyst according to claim 1 or 2, wherein the carrier contains 5 to 20% by weight of silica. 4) The hydrotreating catalyst according to claim 1 or 2, wherein the carrier contains 10 to 16% by weight of silica. 5) Group VI metals of the Periodic Table of Elements are contained in an amount of 5 to 30% by weight as oxides, and Group VIII metals of the Periodic Table of Elements are contained in an amount of 1% by weight as oxides.
The hydrotreating catalyst according to claim 3 or 4, which contains 10% by weight. 6) Hydrogenation treatment according to any one of claims 1 to 5, wherein the metal of group VI of the periodic table of elements is molybdenum, and the metal of group VIII of the periodic table of elements is nickel and cobalt. Catalyst for use.