JPS60220145A - Preparation of hydrogen treating catalyst - Google Patents

Abstract

PURPOSE:To prepare a highly active hydrogen treating catalyst used in the hydrogen treatment of hydrocarbon oil, by supporting a metal belonging to the group VIII and the group VIB of the Periodic Table by a silica-alumina carrier in a well dispersed state. CONSTITUTION:Silica-alumina containing 2-35wt% of silica or a material containing said silica-alumina is used as a carrier and a metal belonging to the group VIII of the Periodic Table such as nickel or cobalt is supported by said carrier as oxide in a range of 0.5-20wt% according to an impregnation method and a metal belonging to the group VIB of the Periodic Table such as molybdenum or tungsten is subsequently supported as oxide by said carrier in a range of 1-8wt%.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a hydrotreating catalyst used for hydrotreating hydrocarbon oil. The present invention also relates to a method for producing a highly active hydrotreating catalyst by supporting a Group VIB metal with good dispersion.

In the description of the present invention, "hydrotreatment" refers to a treatment method by contacting hydrocarbon oil with hydrogen, including hydrorefining with relatively less severe reaction conditions, and some decomposition reactions with relatively more severe reaction conditions. This includes hydrorefining, hydroisomerization, hydrodealkylation and other reactions of hydrocarbon oils in the presence of hydrogen. For example, hydrodesulfurization of distillate oil and residual oil of atmospheric distillation or vacuum distillation, hydrogenated membrane nitrogen,
It also includes hydrorefining of kerosene fractions, gas oil fractions, waxes, lubricating oil fractions, etc.

The catalyst prepared according to the invention is suitable for the hydrodesulfurization of medium distillate oils such as kerosene fractions and gas oil fractions, heavy distillate oils of vacuum distillation, asphalt-containing residue oils or mixtures thereof. This specification is specifically described in connection with hydrodesulfurization because it is suitable for carrying out the process.

Conventionally 1 In hydrodesulfurization during petroleum refining, metals from group Ⅰ of the periodic table and/or metals from group VI of the periodic table are added to an alumina carrier.
For example, cobalt-molybdenum-based or nickel-molybdenum-based hydrogenation catalysts are widely used, which are produced by supporting one or more metals selected from the group B metals. The most important thing in the production of such hydrotreating catalysts is to prepare a carrier with molybdenum-cobalt or molybdenum-nickel particles of uniform composition in a large amount (approximately 20% by weight as oxide) and in a highly dispersed state. It is to make them bear the burden.

Conventionally, (1) coprecipitation method, (2) cross-fertilization method, and (3) impregnation method have been proposed as methods for producing hydrotreating catalysts.
It has been implemented. However, the coprecipitation method has the drawback that when there are multiple active metal components as in the above-mentioned hydrotreating catalyst, it is difficult to uniformly produce these active metal components with good reproducibility. are doing. In the cross-conducting method, as mentioned above, in a hydrotreating catalyst having multiple active metal components, it is necessary to place the carrier and the multiple active metal components sufficiently close to each other and to achieve uniform and complete mixing. However, this kneading method has the disadvantage that it is extremely difficult to achieve such a state. Compared to the above two methods, the impregnation method is more suitable for producing hydrotreating catalysts that have multiple active metal components, such as cobalt-molybdenum-based catalysts using alumina as a carrier, or nickel-molybdenum-based catalysts, as described above. It can be said that

In the production of hydrotreating catalysts by the impregnation method, alumina is usually used as a carrier, molybdenum is first supported on the alumina carrier (step 1), and then cobalt or nickel is added through the interaction between the active metal and molybdenum. A method (two-stage impregnation method) in which molybdenum-cobalt or molybdenum-nickel is supported on a carrier as fine particles (second step) has been proposed, but in the first step approximately 15%
It is difficult to support molybdenum in a highly dispersed state on an alumina carrier, and the dispersibility of the final catalyst is also substantially determined by the state of dispersion of molybdenum in the first step, resulting in a decrease in activity. is forced.

In order to solve the above-mentioned drawbacks of the impregnation method, the first
It is also conceivable to deposit cobalt and/or nickel on the alumina support in a step, followed by the molybdenum, but in this case the active metal components such as cobalt or nickel have sufficient interaction with the alumina support on the alumina support. It has no effect and aggregates as inactive CO3O4, or forms cobalt aluminate and becomes inactive, making it impossible to achieve the desired performance.

Further, the method of simultaneously supporting a plurality of active metals on an alumina carrier by impregnation is not preferable because it is difficult to uniformly distribute each component within the carrier.

As mentioned above, when using a catalyst with a high amount of active metal components supported, such as a catalyst for hydrotreating, and supporting multiple active metal components, each component must be in a uniform composition and highly dispersed state. It is extremely difficult to support this by conventional known methods.

Therefore, the main object of the present invention is to utilize the bonding force between a metal from Group 1 of the Periodic Table of the Elements and a support in a method for producing a catalyst for hydrotreating comprising a metal of Group 1 of the Periodic Table of the Elements and a metal of Group VIB. The object of the present invention is to provide a method for producing a catalyst that obtains a highly active catalyst for hydrogenation treatment by supporting both active metal components in a dispersive manner.

Still another object of the present invention is to apply cobalt or nickel to silica alumina or a carrier containing silica alumina using an ion exchange method with good dispersibility and chemical uniformity (supported conoglutes or nickel). A catalyst for hydrotreating that can improve the uniformity of the bond strength between nickel and a support, and can therefore support molybdenum, the main active metal component, on the support with good dispersion and uniformity. The purpose of this invention is to provide a method for manufacturing the same.

As a result of various research and experiments aimed at improving conventional manufacturing methods, the present inventors have discovered that conolte and nickel, which are the active metal components of hydrotreating catalysts, are supported on the acidic sites of the carrier. By using a silica-alumina carrier or a silica-alumina-containing carrier with acidic points instead of the conventional alumina carrier, cobalt or nickel can be dispersed in the first step! It has been found that it can be supported well and stably. This is thought to be because cobalt or nickel is supported on the acidic sites of silica alumina due to chemical bonding force, and in particular, by supporting cobalt or nickel on a silica alumina support or a silica alumina-containing support using an ion exchange method, it is possible to disperse the cobalt or nickel. I discovered that it can dramatically improve your sexual performance.

Furthermore, molybdenum can be supported in the second step on the silica-alumina carrier or the silica-alumina-containing support on which cobalt or nickel was supported in the first step as described above, and in this case, molybdenum is combined with cobalt or nickel. It was found that molybdenum-cobalt or molybdenum-nickel fine particles were supported uniformly and in a highly dispersed state by being supported around cobalt or nickel by the bonding force of .

As mentioned above, the inventors have found that when silica alumina or silica alumina-containing material is used as a support, cobalt and nickel act as promoters (co-catalysts) and at the same time act as anchors for molybdenum, and molybdenum is an active metal component. It has been found that it has the effect of improving the dispersibility and stability of.

The present invention has been made based on this new knowledge.

To summarize, the present invention uses silica-alumina or silica-alumina-containing material as a support, and first supports one or more metals selected from the group of metals of group Ⅰ of the periodic table of elements on the support, The following is a method for producing a catalyst for hydrotreating, characterized in that one or more metals selected from the group of group VI B metals of the periodic table of elements are supported. In particular, the present invention is characterized in that good catalytic activity is obtained by reducing the amount of group metal supported.

In the method for producing a hydrotreating catalyst according to the present invention, a silica-alumina carrier or a silica-alumina-containing carrier having acidic sites is used instead of an alumina carrier. By using silica-alumina or a silica-alumina-containing material as a carrier, a metal from Group 1 of the Periodic Table of Elements may be supported in the first step.

The active metal component is supported stably with good dispersibility by bonding to the acidic sites of silica alumina. In this way, by supporting the group VIB metal on the acidic sites of the carrier in the Ml step, the main active metal, the group VIB metal of the periodic table, is transferred to the outside of the group metal, that is, at the It can be used as a catalyst for hydrotreating, and is extremely suitable as a catalyst for hydrotreating.

On the other hand, it is important for the catalyst to maintain the desired solid acidity in hydrotreating, especially hydrodesulfurization and hydrogenation membrane nitrogen, and it is known that acidity can be controlled by controlling the silica content in the carrier. ing. In the present invention, if the silica content of the silica-alumina carrier or the silica-alumina-containing carrier is excessive, hydrogen consumption may increase due to excessive decomposition reaction in the hydrodesulfurization reaction or hydrodesulfurization reaction. This results in undesirable reactions such as formation.

Therefore, in the present invention, the silica content in the silica-alumina carrier or silica-alumina-containing carrier is 2 to 35% by weight.
It should preferably range from 5 to 50% by weight, more preferably from 7 to 12% by weight.

Further, the surface area and pore distribution of the silica alumina carrier are not particularly defined, but a surface area preferable as a catalyst carrier, for example, 50 m2/j/ or more, especially 2007F127
g or more is suitable. The method for producing such a silica alumina carrier includes a method in which alumina and silica gels are each prepared in advance and the two are mixed together, or a method in which silica gel is immersed in a solution of an aluminum compound, and then an appropriate amount of K and a basic substance are added. A method of depositing on silica gel such as alumina gel, or a method of adding a basic substance to a homogeneous mixed solution of a water-soluble aluminum compound and a water-soluble silicon compound and co-precipitating both can be adopted.

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 group 1 of the periodic table of elements. That is, one or more selected from group Ⅰ 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 metals of the Periodic Table of Elements. That is, one or more selected from Group VIB chromium, molybdenum, and tungsten are used. Preferably molybdenum and tungsten will 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 Ⅰ and Group VIB above are:
It is preferable to support it as an oxide and/or a sulfide. The supported amount of the active metal component is based on the catalyst as an oxide, and the Group VIB metal is (L5 to 20% by weight, preferably 1 to 8% by weight, more preferably 2 to 5% by weight, The group metal is 5-30% by weight, preferably 8-251%
% by weight, more preferably 15 to 20% by weight. If less than 5% by weight of the group metal is supported, sufficient catalyst cannot be obtained, and if the metal is supported by more than 20% by weight, free metals that do not bond with the carrier may be used. When the free component of the Group 1 metal increases, an inert composite oxide is formed when a Group VIB metal is supported next, reducing the dispersibility of the Group VIB metal and reducing the catalyst. Reduces activity.

On the other hand, if the Group VIB metal is less than 5% by weight, activity is obtained, but if it is more than 30% by weight, the dispersibility decreases and at the same time the first
The promoter effect of group metals is not exhibited.

In the present invention, as a method for supporting the active metal component on the carrier in the first and second steps, an impregnation method is adopted in which the carrier is immersed in an aqueous solution of a soluble salt of the metal and the metal component is introduced into the carrier. I can do it. The impregnation operation is as follows:
The carrier is immersed in an impregnating solution at or above room temperature and maintained under conditions such that the desired component is 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 carrier to be immersed in the impregnating solution is determined depending on the amount of carrier supported.

On the other hand, the present inventors have discovered that the first step in the catalyst production method according to the present invention is an ion exchange method in which protons on the surface of a silica-alumina carrier or a silica-alumina-containing carrier are exchanged with the metal ions via ammonium ions. It has been found that this is extremely suitable. It has been found that when the present invention is carried out based on the ion exchange method, the degree of dispersion of the catalyst is significantly improved compared to that of a conventional impregnation method catalyst, and the chemical uniformity is also improved.

A method for producing a catalyst based on an ion exchange method is carried out by preparing an ammine complex salt solution of an active metal, immersing a silica alumina support in the solution, and supporting the metal support. The appearance and concentration of the ammine complex salt solution can be adjusted as appropriate so that a desired amount of metal is supported.

After the carrier supporting the hydrogenation-active metal component is separated from the impregnating solution, it is washed with water, dried, and calcined.

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

The catalyst produced according to the present invention shows little activity deterioration and
A high desulfurization rate can be achieved even under less severe reaction conditions, especially at lower reaction pressures.

For hydrodesulfurization, the catalyst can be used in any of fixed bed, fluidized bed, or moving bed formats, but it is preferable to use a fixed bed reaction column from the viewpoint of equipment and operation. Furthermore, it is also possible to achieve a high desulfurization rate by combining two or more reaction towers to perform hydrodesulfurization. It can also be used to fill a guard drum for the purpose of metal removal prior to the tower.

Preferably, the catalyst is presulfided before use. Presulfurization can be carried out in situ in the reaction column. That is, the calcined catalytic sulfur-containing distillate and the temperature;
Approximately 150 to 400°C, pressure (total pressure); approximately 20 to 100 to 9/crn2, liquid space velocity; approximately cL3 to 2.0 ■/H/
Contact is made in the presence of a hydrogen-containing gas of about 50 to 5001/l, and after the sulfidation treatment is completed, the sulfur-containing distillate is switched to feedstock oil, and the operating conditions are set appropriate for desulfurization of the feedstock oil, and operation is started. .

In addition to the methods described above, the sulfurization treatment may be carried out by directly contacting hydrogen sulfide or other sulfur compounds with the catalyst, or by adding it to a suitable distillate and bringing it into contact with the catalyst.

The present inventors researched the method for producing the catalyst according to the present invention as described above and conducted various experiments. As a result, the present inventors found that according to the method for producing the catalyst according to the present invention, the catalyst contains about 2 to 35% by weight of silica. On the alumina support, one or more metals selected from the group of metals of Group I of the Periodic Table of Elements and metals of Group V [B of the Periodic Table of Elements]
one or more metals selected from the group metals; 70% of volume
The volume of pores with a diameter in the range of 100 to 300 μm is approximately 3 of the volume of pores with a diameter in the range of 0 to 600 μm
0% or less (pore volumes of ■ and ■ above are measured by nitrogen adsorption method) ■ 150 to 150,000 measured by mercury intrusion method
The volume of pores with diameters in the human range is approximately 0. O05~
o, 2sil/, li', preferably 0.1 d/"
, 9 or less ■ 150 to 2.0 measured by mercury intrusion method
The volume of pores with diameters in the range of 000R1
/g or less ■ The volume of pores with diameters in the range of 0 to 300 measured by nitrogen adsorption method is approximately 0.30 to 070 at/g.
Range of fl It has been found that it is possible to suitably produce a catalyst for hydrotreating hydrocarbon oil having a specific surface area in the range of about 200 to 400 m27 g. Moreover, the total pore volume of the catalyst; α4~αq y
nl/fl, bulk density: about 15 to tOF, side fracture strength: about 08 to 15 kg/m.

Conventionally, hydrodesulfurization methods for residual oil have been actively developed with the aim of reducing the amount of sulfur dioxide released, as sulfur compounds in petroleum fuel become sulfur dioxide gas when burned, becoming one of the sources of air pollution. Many proposals have been made. For example, in order to perform hydrodesulfurization and hydrogenation membrane nitrogen of hydrocarbon oil containing asphalt and metal-containing compounds,
Anticipating that the pore distribution of the hydrorefining catalyst used would have a large effect on the activity and activity maintenance ability, the pore radius was set at 80 Å to prevent asphalt and metal-containing compounds from penetrating into the feedstock oil. The pore volume is 10% of the total pore volume.
In the method of using a catalyst having a pore distribution suppressed to below (Japanese Patent Publication No. 45-38142) or in the hydrodesulfurization of the same residual oil, the volume of pores with a radius of 120 Å or less is relatively uniform at intervals of 10 people. A method using a distributed catalyst (Japanese Patent Publication No. 45-58143) is known. Also, crude oil or prefixed crude oil, in which the pore volume of particles having a pore size in the range of about 50 to 100 pores is at least 50% of the total volume, and the pore volume of particles with pore sizes in the range of 0 to 50 pore size is up to 25% of the total volume. A hydrodesulfurization catalyst has also been disclosed (Japanese Unexamined Patent Publication No. 1987-1
Publication No. 0556).

However, in these hydrodesulfurization methods, the pore distribution of so-called macropores with a pore radius of 300λ or more of the catalyst used has not been sufficiently studied, and its influence on catalyst performance is ignored. In other words, the conventionally disclosed technology has focused on so-called micropores, but micropores alone have a large amount of sulfur content, crab element content, and metal content, such as atmospheric distillation residue oil, vacuum distillation gas oil, vacuum distillation residue oil, etc. However, the activity and activity maintenance ability of hydrogenated hydrocarbon oil containing asphalt and other impurities cannot be improved.

The inventors have discovered that the pore distribution across both the microbore and macrobore regions of the catalyst has a profound effect on desulfurization and denitrification. That is, the pore volume of a person with a pore diameter of 150 to 2,000 as measured by mercury porosimetry is approximately 0.
01 m/g or less, and the volume of pores with a diameter in the range of 50 to 100 measured by nitrogen adsorption method is 0 to 100 m/g.
70% or more of the volume of pores having a diameter in the range of 150 people, preferably more than aoX, more preferably more than qox, and furthermore the volume of pores having a diameter in the range of 100 to 600 people It has been found that a catalyst having a diameter in the range of 30% or less, preferably 20% or less of the volume of pores exhibits a very significant 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. In order to prevent this, it is necessary to reduce the pore volume of the macrobore.

In addition, in order to suppress the lightening of hydrocarbon oil due to carbon-to-carbon cleavage of saturated hydrocarbons and to prevent the pores of the catalyst from being blocked by asphalt and resin components, it is preferable to reduce pores with a diameter of 30 Å or less. That's why.

It is already known that solid acids such as alumina silica are suitable catalyst components for desulfurization and denitrification reactions of hydrocarbon oils, but in hydrorefining, it is necessary to maintain the desired solid acidity as described above. is important, and for this purpose acidity can be controlled by controlling the silica content. The present inventors have recognized that the catalytic ability and selectivity of the hydrogenation reaction of hydrocarbon oil can be adjusted by adjusting the cracking activity based on acidic control by controlling the silica content in the carrier and by specifying the pore structure of the catalyst. 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 generation of carbon components associated with the decomposition reaction. and plays an extremely important role.

Therefore, in the hydrodesulfurization reaction or hydrodenitrogenation reaction, as mentioned above, in order to control the increase in hydrogen consumption or the formation of coke due to excessive decomposition reaction, the silica content in the alumina-containing carrier must be controlled. should range from about 2 to 35'M weight percent, preferably from about 5 to 30 weight percent.

Although the pores of the above-mentioned hydrotreating catalyst are concentrated in a range of 60 to 100 diameters as measured by the nitrogen adsorption method, the pores are distributed over a fairly wide range as a whole.

The reason why such a pore distribution of the catalyst disclosed by the present invention imparts a remarkable effect on the activity and activity maintenance ability in hydrodesulfurization of hydrocarbon oil is not fully elucidated. As a result of extensive research, asphalt, resin content, and metal-containing compounds in raw oil are
When attached to the catalyst surface, the pores with extremely small pore diameters are blocked and the active sites of the catalyst are completely isolated. However, if the pore diameter is increased within a certain range, metal-containing compounds, that is, asphalt Alternatively, the resin may similarly adhere to the catalyst surface, but not completely block the pores, allowing hydrocarbon molecules and sulfur molecules that then reach the catalyst to approach the active sites, thus achieving high performance. It can be assumed that the

The support used in the catalyst of the present invention contains about ~% by weight of silica.
It is alumina or alumina-containing substance containing alumina. The alumina-containing material is a composition obtained by blending alumina with another carrier material, for example, one or more of magnesia, calcium oxide, zirconia, titania, boria, hafnia, crystalline zeolite, etc. is added to alumina. Can be blended. As mentioned above, the silica is suitable for controlling the solid acidity of the catalyst.
~% by weight, preferably in the range of ~% by weight. A more preferred silica content is in the range of about 7-12% by weight.

Silica provides strong acid sites to the catalyst and increases the decomposition activity of the catalyst, whereas magnesia, for example,
It has the effect of reducing the strong acid sites possessed by silica and the like, and at the same time increasing the weak acid sites, thereby improving the selectivity of the catalyst. The magnesia, calcium oxide, zirconia, titania,
The blending amount of refractory inorganic oxides such as boria, nophnia, and crystalline zeolite is about 1 to 1 to alumina-silica.
A range of 10% by weight is suitable.

As alumina, γ-alumina, χ-alumina or η
- Alumina or mixtures thereof are suitable. The method for producing the silica-alumina support or the silica-alumina-containing support is as described above. The manufacturing conditions such as temperature and time for precipitation and aging of alumina and silica hydrates are adjusted to obtain the desired product.

Water-soluble compounds, such as water-soluble acidic aluminum compounds or water-soluble alkaline aluminum compounds, specifically, aluminum sulfates, chlorides, nitrates, alkali metal aluminates and aluminum, as raw materials used in the production of catalysts. Alkoxides and other inorganic or organic salts can be used. As a water-soluble silicon compound, alkali metal silicate (Na20:5iO2=1:2
~1:4 is preferred. ), yh-aralkoxysilanes, orthosilicate esters, and other silicon-containing compounds are suitable. These aluminum and silicon compounds can be used as an aqueous solution, and the concentration of the aqueous solution is not particularly limited and may be determined as appropriate, but the concentration of the aluminum compound solution is approximately 0.01 to 4.0%. It can be employed within the range of 0 mol. A preferred method for producing a catalyst containing an alumina-silica carrier or other carrier material is a co-precipitation method of alumina and silica, but deposition methods, gel mixing methods, etc. can also be employed.

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

After adding an alkaline hydroxide solution to an acidic aluminum aqueous solution (preferably in the range of about 0.6 to 2 mol) and an alkaline aluminate solution and heating to about 50 to 98 °C at a pH of 6,0 to 1 tO, the silicic acid Add an aqueous alkali solution to adjust the pH to about &0 to 11.0, preferably about &
Hydrogel or hydrosil is produced in the range of 0 to 10.5, or by adding ammonia water, nitric acid or acetic acid as appropriate, and heating this suspension to a temperature of about 50 to 98 °C while adjusting the pH. Hold for 2 hours. In this case, an even better catalyst support can be obtained by adding oxycarboxylic acid or a salt thereof, such as tartaric acid, citric acid, other hydroxyl polycarboxylic acids, and alkali metal salts. It is also possible to use aminodical acids and their salts, such as glutamic acid, aspartic acid and other amino group-containing polycarboxylic acids and alkali metal salts. These compounds can be added in an amount of α0002 to 0.1 mol per mol of the aluminum compound. After this process is finished,
The precipitate is separated by F, washed with ammonium acetate and water to remove impurity ions, and finished into a carrier by conventional methods such as drying and calcination.

Drying is carried out by heating from room temperature to about 200°C in the presence or absence of oxygen, and calcination is carried out by heating to a temperature in the range of about 200 to 800°C in the presence of oxygen.

The hydrogenation-active metal component supported on the carrier is as described above. In particular, for the hydrodesulfurization of hydrocarbon oils, combinations of Group VIB metals and Group 1 metals, such as molybdenum-cobalt, molybdenum-nickel, tungsten-nickel, molybdenum-cobalt-nickel or tungsten Combinations such as -cobalt-nickel can be preferably used. These active metal components Km3
It is also possible to add metals such as metals from group 1 of the periodic table, such as manganese, and metals from group 1, such as tin and germanium. These third metals
It can be added as a pre-treatment of the carrier before the step or as a post-treatment after the second step.

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

The hydrogenation active metal component is supported on the carrier in the first and second steps as described above.

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 I15~5
．． A range of OIllm 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 heavy hydrocarbon oils, the catalyst is
Prior to use, it is preferable to carry out presulfurization as described above.

Regarding the amount of supported metal components, the Group Vl metal may be supported as an oxide in an amount of about 1 to 20% by weight based on the catalyst, and the Group VIB metal may be supported in an amount of about 5 to 30% by weight.

As described above, the catalyst produced in this manner comprises at least one hydrogenation-active metal component supported on alumina or an alumina-containing support containing about 2 to 55% by weight of silica; The volume of pores with diameters ranging from 100 to 70X the volume of pores with diameters ranging from 0 to 150
More than ■ The volume of pores with a diameter in the range of 100 to 300 μm is approximately 6 of the volume of pores with a diameter in the range of 0 to 500 μm
0% or less (pore volumes of ■ and ■ above are measured by nitrogen adsorption method) ■ 150 to 150,000 measured by mercury intrusion method
The volume of pores with diameters in the human range is approximately 0.005 to 0.
．． 25 ydl & preferably o, 1 ml/
g or less ■ 150 to 2.00 measured by mercury intrusion method
The volume of pores with diameters in the range of approximately 0.0111
11711 or less ■ The volume of pores with diameters in the range of 0-300 measured by nitrogen adsorption method is approximately 0.50-070 IrLl/
g range and (1) specific surface area in the range of approximately 200 to 400 m2/9, and total pore volume;
0.9 m/g, bulk density; approximately 0.5~toy7m
1, side breaking strength: about 0.8 to 5.5 to 97 m, realizing a good hydrorefining catalyst 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) (1,959) P, H, Errm
ett, 5tal, ``Catalysis',
1, 125 (1959) ('Re1nhold
Publishing Co.) and the method described in Catalyst Engineering Course, Volume 4, Pages 69 to 78 (published by Chijinshokan) (1968).

In the mercury intrusion method, the contact angle of mercury to the catalyst is set to 14
0°, surface tension of 480 dynes/cIIL, and all pores were assumed to be cylindrical.

Various correction methods based on multimolecular layer adsorption have been proposed for the nitrification adsorption method, among which the BJH method (E, P,
Barreff, L.G., Joyner and
P, P, Halnda, J, Amer,, Ch.
Em, Soc, 73.375 (1951)) and the CI method (RoW, Cranston and F, A
, Inkley.

@Advances in Catalysis, ”
IX r 145 (1957) (New York
Academic Press ) is commonly used.

The data related to the pore volume in the present invention uses the adsorption side of the adsorption equimixture, and is calculated using the DH method (D, Dollimorean
d G, R, Heal, J, Appl, Chem
, 14.109 (1964)).

A method for hydrodesulfurization of hydrocarbon oil using a catalyst prepared according to the present invention is described.

As the heavy hydrocarbon oil, vacuum distilled gas oil, 1L cracked oil, etc. can be used. Vacuum distilled gas oil is a distillate oil containing a fraction having a boiling point in the range of about 250°C to 560°C, which is obtained by distilling atmospheric distillation residue oil under reduced pressure, and has a sulfur content,
It contains considerable amounts of nitrogen and metals. For example, to take an example of vacuum distilled light oil from Middle East crude oil, approximately 2 to
Contains 4% by weight sulfur and about 105-12% nitrogen-type blades. It also contains 0.405% by weight of residual carbon.

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

Further, the hydrocarbon oil contains sulfur, nitrogen, asphalt, and metal-containing compounds, has a boiling point substantially above about 480°C, and contains residual oil from normal pressure or vacuum distillation of crude oil. For example, a residual oil containing about 50 to 100% by weight of hydrocarbon components having a boiling point of about 480°C or higher at normal pressure usually has a sulfur content of about 1 to 10% by weight;
Nitrogen content of about 0.1-1% by weight, about 10-1. OOOp
pm metals and approximately 1% by weight residual carbon (Conradson).

As the raw material oil for the hydrorefining method, the above-mentioned atmospheric distillation residue oil, vacuum distillation residue oil, vacuum distillation light oil, cracked oil, normal pressure distillation light 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, reaction temperature: about 350-450°C, reaction pressure: about 30-200°C.
kg/(:IIL2, hydrogen-containing gas rate; approx. 50-1
．． 500)/l, and liquid space velocity; approximately α2~2. O
Adopt V/H/V. The hydrogen concentration in the hydrogen-containing gas j may range from about 60 to 100X. Second, the catalyst produced according to the present invention exhibits little activity deterioration and can achieve high desulfurization rates even under less severe reaction conditions, particularly at lower reaction pressures.

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 in terms of equipment or operation. preferable. Furthermore, a high desulfurization rate can be achieved by combining two or more reaction towers for 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 carrying out desulfurization and denitrification reactions.

Next, examples of the present invention will be described.

Example 1.2.6 Cobalt nitrate) 1&91 was dissolved in 70 pnl of distilled water, and 5 otrrl of ammonia was added thereto to obtain a cobalt ammine complex salt solution. Add this solution to the silica aluminum carrier (
50 g of silica (silica content 10%) was crushed for 16 hours to retain 5% by weight of cobalt as cobalt oxide. 30 minutes after air drying
The catalyst calcined at 0°C was used as a catalyst (Example 1), the one calcined at 500°C was used as Catalyst B (Example 2), and the one calcined at 600°C was used as Catalyst C (Example 3).

Comparative Example 1.2 Using a commercially available alumina carrier, 5% by weight of cobalt was supported as cobalt oxide in the same manner as in Example 1. Catalyst D (Comparative Example 1) and 600°C were calcined at 500°C.
This was designated as Catalyst E (Comparative Example 2).

Of the catalysts obtained in Example 1.2.3 and Comparative Example 1.2,
In order to understand the supported state of cobalt oxide, analysis was performed using temperature programmed reduction method. The procedure was developed by J.D. Jenkins (CI-IEMTgC).
HVol 7.316-520, (1977)). The results are shown in FIGS. 1 to 5.

Cobalt oxide on an alumina support is either in a state where it undergoes reduction at temperatures below 300°C (considered to be cobalt oxide fine particles that have no bond with the carrier), or in a state where it does not undergo reduction at 700°C (such as cobalt aluminate, which is strongly linked to alumina). (considered to be combined cobalt oxide). Most of the catalysts fired at 300°C are the former, and catalysts E fired at 600°C are mostly the latter. Even at intermediate firing temperatures, only the ratio between the two changes, and cobalt oxide in other states is not found.

On the other hand, on the silica-alumina support, the two states of cobalt oxide observed in the case of the alumina support are rather small, and the cobalt oxide that undergoes reduction at 500-700°C (cobalt oxide moderately bound to the support) is large. The effect of firing temperature is smaller than in the case of alumina carriers.

The above results show that the supported state of cobalt oxide, which is one of the active metals, is completely different between the silica alumina carrier and alumina, which is widely used as a carrier for desulfurization catalysts. When using
This suggests that a new catalyst production method that takes advantage of such percentage characteristics is possible.

Example 4 The same procedure as in Example 1 was carried out using an aqueous cobalt nitrate solution instead of the cobalt ammine complex salt solution, and the same silica alumina support was used to replace cobalt with cobalt oxide.
It carried wtx. Catalyst P has a firing temperature of 500°C.

The analysis results of catalyst F by the temperature program reduction method are shown in FIG. Compared to catalyst B, it showed a slightly more complex profile, indicating that the supported state was non-uniform.

Comparative Example 5.4.5.6 Four types of cobalt-molybdenum catalysts were produced using silica-alumina as a carrier containing 25% silica.

Catalyst G (Comparative Example 6) - Ammonium Molybdate 13.
Dissolve 2Jl' in 50g of 3N ammonia water.

A silica alumina carrier 25. After soaking li+ for 2 hours, discard the liquid and air dry. After firing at 550° C., cobalt was supported in the same manner as in Example 4. After air drying 5
Catalyst G was obtained by firing at 50°C.

Catalyst H (Comparative Example 4) - Molybdenum was supported in the same manner as in Catalyst G, and then calcined at 550°C, and cobalt was further supported in the same manner as in Example 1 using a cobalt ammine complex salt solution. After air drying, catalyst H was obtained by calcining at 550°C.

Catalyst (Comparative Example 5) - 15.9 g of copal nitrate was dissolved in 70 g of distilled water. Add 80 grams of ammonia to this solution. Furthermore, ammonium molybdate 2 & 4.9 was dissolved in this. A silica-alumina carrier soy was immersed in this solution, and after being left for 2 hours, the solution was discarded, air-dried, and then calcined at 550°C to obtain a catalyst (2).

Catalyst J (Comparative Example 6) - 280 y of phosphomolybdic acid was dissolved in 150 ml of ethanol. Cobalt nitrate 2z is added to this solution.
79 was further dissolved. Silica alumina carrier 5 is added to this solution.
After soaking 0g and leaving it for 2 hours, discard the liquid and air dry.
Catalyst J was obtained by firing at 550°C.

Example 5.6 Catalyst K (Example 5) A cobalt cobalt was carried out in the same manner as in Example 1 using a cobalt ammine complex salt solution. After air drying, it was calcined at 550°C, and further immersed in a 3N ammonia solution of ammonium molybdate to support molybdenum. After air drying, it was calcined at 550°C to obtain catalyst K.

Catalyst L (Example 6) Cobalt was supported using a cobalt nitrate aqueous solution in the same manner as in Example 4.

After air drying, it was fired at 550°C, and then in the same manner as in Example 7,
A catalyst was obtained by supporting molybdenum.

The desulfurization activity of catalysts G, H1, J, and L was investigated by desulfurization reaction of thiophene.

Feed composition is thiophene a 5 wtX, pyridine 2
, 5 wtX, n-hexane 92.2 wtX. The reaction conditions are as follows.

Reaction temperature 500°C Reaction pressure Atmospheric pressure Feed flow rate isW/H/W Hydrogen/feed molar ratio 6.0 Table 1 The above results show that in the catalyst according to the present invention on an alumina support containing silica, L was prepared by other methods. It can be seen that the activity is significantly higher than that of catalysts G, H, I, and J.

Comparative Example 7.8, Examples 7 to 15 Nickel molybdenum catalysts (M-tJ) were prepared using nine types of silica-alumina carriers having different silica contents.

The loading procedure was similar to Example 5 (Catalyst K) except that a nickel ammine complex salt was used.

The performance of these catalysts was evaluated by desulfurization reaction of Middle East Y-pressure distillate oil. The reaction conditions are as follows.

Reaction temperature ('C)! +20 Reaction pressure (2 to ψ) 50 Catalyst loading amount (m/) 12 Feed flow rate (V/H/V) α8 1-12/Feed ratio (SCF/B) 2500 From the above results, it can be seen that the preparation method according to the present invention It can be seen that a silica-alumina carrier containing 2 wtX or more and 55 wtX or less of silica is highly effective in improving the desulfurization and/or denitrification activity of the cobalt-molybdenum or nickel-molybdenum catalyst used.

Example 14 9.7 g of cobalt nitrate) and nickel nitrate T49 were dissolved in 70 d of distilled water, and a silica-alumina carrier 50I containing 10% by weight of silica was immersed in this solution for 12 hours to dissolve each of cobalt and nickel as oxides. It carried 35% by weight and α5 heavy type blade. The carrier supporting cobalt and nickel was air-dried and calcined at 550°C, and then immersed in a 3N ammonium molybdate aqueous solution to support 15% by weight of molybdenum as molybdenum oxide to obtain catalyst (2). The results are shown in Table 3. Co-Ni-Mo according to the invention
It can be seen that the catalysts of the system also exhibit excellent desulfurization and denitrification rates.

Example 15 Catalyst W was prepared under the same conditions and operations as in Example 9 except that tungsten was used instead of molybdenum. A solution of ammonium tungstate dissolved in distilled water was used to support tungsten. The results for catalyst W are shown in Table 3. It can be seen that the N1-W based catalyst according to the present invention also exhibits excellent desulfurization and denitrification rates.

Example 16 4.81 ml of pure water was heated to about 70°C, and a sodium aluminate solution (170.4 p of sodium aluminate, 235.1 ec of pure water) and an aluminum sulfate solution (249.59 ml of aluminum sulfate, pure water) were added. After adding 450.5 CC), adjust the pH to 8 with sodium hydroxide solution or nitric acid solution.
．． It was cut into 8 to 9.2 KM knots and aged at about 70°C for about 1 hour.

To this, sodium silicate solution (No. 5 water glass SO,
sg, 1294 g of pure water) was added, and a nitric acid solution was added as necessary to adjust the pH to about 9, and the mixture was aged at a temperature of about 70° C. for 3 hours.

The resulting slurry is filtered, and the cake that is taken from house to house is re-sludged with a 15% ammonium carbonate solution, filtered, and then transferred to liquid F.)
It was washed with an ammonium carbonate solution until the IJium concentration became less than s ppm. After drying this at 100° C. for 16 hours, pure water and a small amount of vinegar were added, and the mixture was kneaded while drying until it had a water-containing ftK that could be molded, and was molded into a cylindrical shape of 15 m 11 m φ using an extrusion molding machine. The molded pellets were dried at 100°C for 16 hours and further heated at 600°C.
It was fired at ℃ for 5 hours to obtain a carrier.

On the other hand, nickel and molybdenum were supported in the same manner as in Example 9, except that a nickel ammine complex salt solution prepared by dissolving nickel nitrate in distilled water and adding ammonia thereto was used. That is, the aforementioned silica alumina carrier (silica content: 10 weight x) was added to a nickel ammine complex salt solution of 50. F was immersed for 16 hours to support 4% by weight of nickel as nickel oxide. The carrier carrying nickel was air-dried, then calcined at 550°C, and then immersed in a normal ammonium molybdate aqueous solution to carry 14% by weight of molybdenum as molybdenum oxide. After air drying this, 55
A catalyst was obtained by firing at 0°C. This will be referred to as catalyst X. The physical properties of this catalyst are shown below.

Physical properties Specific surface area (m2/, 9) 265 Bulk density (J/mj) (L72 Side fracture strength (ky/m) 52 Catalyst particle diameter (longest) (■) is Pore volume CR6/9> 30 Å or less ( LOO2 50-100λ G, 389 100-300 people 0.072 0-150 people 0.0425 0-300 people 0-465 600λ or less (nitrogen gas adsorption method) 0.525150-
150,000 people (mercury intrusion method) α021150-2,
000 people (mercury intrusion method) α008PV (x Ro~1
o o )/PV(o~150)×100 9t5PV
(ioo ~5oo)/PV(o ~5oo)xtoo
15.3 Catalysts N-T of Examples 7-13 were prepared using commercially available silica-alumina supports, e.g. catalyst P of Example 9 with a silica content of 10% by weight had the following physical properties: It had

Physical properties Specific surface area (m2/g) 219 Bulk density (9/g) 0.84 Side breaking strength (kg/+a+) t q Catalyst particle diameter (longest) (+w) t5 Pore volume (17g) Pore diameter ( λ) 60 people 0.058 50-100λ 0.189 100-300 people 0.118 0-150 people 0.284 0-300 people CL565 600λ or less 0.517 150-150,000 people 0.026150-2,0
00 people 0.01! I PV(30~1oo)/PV(o~1so)X1oo
66.5PV (10t!+00)/PV (Q~30
0)

Example 17 9.5 g of cobal nitrate and 17 g of nickel nitrate were dissolved in distilled water at 70 dVc. [, to which ammonia 80-
was added to obtain a cobalt-nickel mixed ammine complex salt solution. 50 g of a silica-alumina carrier containing 10% silica was immersed in this solution for 16 hours to support 54% by weight and 0.6% by weight of cobalt and nickel as oxides, respectively. After air drying and calcination, 14% by weight of molybdenum was supported as an oxide in the same manner as in Example 14 to obtain catalyst Y.

Table 3 Examples 18 to 28 The amount of hydrogenation-active metal supported was varied and the relationship between the amount of hydrogenation-active metal supported and catalytic activity was investigated. The results are shown in Table 4. From Table 4, it can be seen that the supported amount of Group 1 metal is 0.5 to 20% by weight, and the supported amount of Group VIB metal is 5 to 30% by weight.

Example 29 Good results were obtained when hydrogenation treatment was carried out using the above-mentioned catalysts Y and V using the atmospheric pressure gas oil fraction of Middle Eastern crude oil as feedstock oil under the following reaction conditions.

Reaction conditions Reaction temperature (℃) 300 Reaction pressure (k57/m3G) 1゜ Liquid space velocity (V/H/V) o, s Hydrogen to raw oil flow rate ratio (SCF/B) 8o.

Raw material oil properties Specific gravity 15/4℃ 0.845f Sulfur content 107 Nitrogen content 58ppm

[Brief explanation of drawings]

Figures 1 to 6 show the analysis results based on the temperature programmed reduction method to show the supported state of cobalt oxide after the first step treatment by ion exchange method according to the method of the present invention using a silica alumina carrier. 1 graph. FIGS. 4 and 5 are graphs showing the analysis results based on the temperature-programmed reduction method to show the state of cobalt oxide supported on an alumina carrier in which cobalt was supported by an ion exchange method. FIG. 6 is a graph showing the analysis results based on the temperature programmed reduction method to show the state of cobalt oxide supported after the first step treatment by the impregnation method according to the present invention using a silica alumina support. First drawing number! 'C 'A 3 1 Soon 1? C Figure 4 Kodo 0 C Z To 55 Figure 6 1', 71 1 Roki・C Proceedings Supplement iE, Book August 28, 1980 Commissioner of the Patent Office Manabu Shiga Case Display 1982 Patent Application No. 76268 Name of the No. Invention Relationship with the Case of Person Amending the Manufacturing Process of Hydrotreating Catalyst Address of Patent Applicant No. 1 #1, Tsubashi-chome, Chiyoda-ku, Tokyo Name Title
Toa Fuel Industry Co., Ltd. Agent address: Postal code: 105 Suzue Building, 5-14-2 Shinbashi, Minato-ku, Tokyo (Telephone: 459-8309) July 31, 1980 (Shipping date) Statement subject to amendment

Claims (1)

[Scope of Claims] 1) Using silica-alumina or a silica-alumina-containing material as a carrier, first, one or more metals selected from the group of metals of group Ⅰ of the periodic table of elements are supported on the carrier, A method for producing a hydrotreating catalyst comprising supporting one or more metals selected from the Group VIB metals of the Periodic Table of the Elements. 2) The method according to claim 1, wherein the metals of Group I of the Periodic Table of the Elements consist of nickel and cobalt, and the metals of Group Vt B of the Periodic Table of the Elements consist of molybdenum and tungsten. 5) The method according to claim 1, wherein the carrier contains 2 to 35% by weight of silica. 4) The method according to claim 1, wherein the carrier contains 5 to 50% by weight of silica. 5) The method according to claim 1, wherein the carrier contains 7 to 12% by weight of silica. 6) Group Ⅰ metals of the periodic table of elements are 0.5 to 20 as oxides.
The method according to claim 3, 4 or 5, wherein the metal of Group VIB of the Periodic Table of Elements is contained in an amount of 5 to 30% by weight as an oxide. 7) 1 to 8% by weight of Group 1 metals of the Periodic Table of Elements as oxides
contained in the periodic table of elements [Group B metals are 8 as oxides]
5. The method according to claim 6, 4 or 5, wherein the content is 25% by weight. 8) 2 to 5% by weight of Group Ⅰ metals of the Periodic Table of Elements as oxides
Group VIB metals of the Periodic Table of Elements are contained as oxides of 1
Claim 3 containing 5 to 20%
4. The method according to paragraph 4 or paragraph 5. 9) Using silica alumina or a silica alumina-containing material as a carrier, first immerse the carrier in an ammine complex salt solution of one or more metals selected from the group of group Ⅰ metals of the periodic table of elements. Support the metal by ion exchange method,
For hydrogenation treatment, the metal is further supported by air-drying and firing, and then immersed in a solution of a soluble salt of one or more metals selected from the group of Group VIB metals of the Periodic Table of Elements. Catalyst manufacturing method. 10) The method according to claim 9, wherein the metals of group 1 of the periodic table of the elements consist of nickel and cobalt, and the metals of group VIB of the periodic table of the elements consist of molybdenum and tungsten. 11) The method according to claim 9, wherein the carrier contains 2 to 35% by weight of silica. 12) The method according to claim 9, wherein the carrier contains 5 to 30% by weight of silica. 13) The method according to claim 9, wherein the carrier contains 7 to 12% by weight of silica. 14) Group Ⅰ metals of the periodic table of elements are formed as oxides [lL5~
20% by weight, and the method according to claim 11, 12 or 1!1, wherein the Group VIB metal of the Periodic Table of Elements is contained as an oxide in an amount of 5 to 60% by weight. 15) The metal of group Ⅰ of the periodic table of elements is contained in an amount of 1 to 8% by weight as an oxide, and the metal of group VIB of the periodic table of elements is contained as an oxide of 8 to 25% by weight.Claim 3
4. The method according to paragraph 4 or paragraph 5. 16) The metal of Group 1 of the Periodic Table of the Elements is contained in an amount of 2 to 5% by weight as an oxide, and the metal of Group VIB of the Periodic Table of the Elements is contained in an amount of 15 to 20% by weight as an oxide. , the method according to item 12 or 13.