JP2005296867A - Hydrocarbon hydrotreating catalyst composition and hydrocarbon oil hydrotreating method using the catalyst composition. - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To produce a catalyst composition for hydrotreating hydrocarbon oil, which is used for hydrotreatment of hydrocarbon oil containing metallic compounds such as vanadium and nickel in large quantities and which has both high demetalization and desulfurization activities, and to provide a method for hydrotreating hydrocarbon oil using such catalyst composition. <P>SOLUTION: The catalyst composition for hydrotreating hydrocarbon oil contains a particulate manganese compound in the catalyst composition comprising a hydrogenation-activating metallic component carried by a carrier. THe method for hydrotreating hydrocarbon oil uses such catalyst composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a hydrotreating catalyst composition for hydrocarbon oils, and more specifically, it is used for hydrotreating hydrocarbon oils containing a large amount of metal compounds such as vanadium and nickel, and the desulfurization activity is high without decreasing. The present invention relates to a hydroprocessing catalyst composition for hydrocarbon oils that exhibits demetalization activity.

A conventional hydrotreating catalyst is a metal that is used in industrial equipment for hydrotreating hydrocarbon oils (hereinafter sometimes referred to as heavy oil) containing a large amount of metal compounds such as vanadium and nickel. The catalyst pores are blocked by a compound or the like, and the desulfurization activity and demetallization activity are deactivated, so that there is a problem that the operation cannot be performed for a long time.
Also, in refineries that have fluid catalytic cracking (FCC) equipment downstream of the hydrotreating equipment, the product oil obtained by hydrotreating is used as the feedstock for catalytic cracking. If the removal of the catalyst is not performed sufficiently, a metal compound such as vanadium or nickel contained in the product oil poisons the FCC catalyst and deactivates the FCC catalyst, resulting in an increase in the amount of FCC catalyst used. For this reason, there has been a demand for a hydrotreating catalyst composition that performs desulfurization and demetalization more effectively when hydrotreating heavy oil in a hydrotreating apparatus.

  Various hydroprocessing catalyst compositions have been proposed in response to the aforementioned needs. For example, Patent Document 1 includes an amorphous sulfide of iron and at least one metal selected from the group consisting of Mo, W, and mixtures thereof in a selective hydrodenitrogenation process of a hydrocarbon feedstock. The use of a catalyst is described, wherein the catalyst includes at least one metal sulfide of a promoter metal selected from the group consisting of Ni, Co, Zn, Mn, Cu, and mixtures thereof, providing a hydrocarbon feed It is disclosed that it has an excellent effect on selective removal of nitrogen from a raw material.

  In US Pat. No. 5,689,059, a catalyst comprising at least one element of Group VIIB and its use in hydroprocessing, it comprises at least one matrix, at least one metal of Group VIIB, and at least of Group VIII. In a group consisting of one non-noble metal, at least one Group VIB metal selected from the group consisting of molybdenum and tungsten, and optionally at least one element from Group VIIA, and phosphorus, boron or silicon And a catalyst consisting of an additional element that improves the activity of the catalyst is described, wherein at least one metal of Group VIIB is preferably rhenium or manganese.

Japanese Patent Laid-Open No. 61-162590 JP-T-2001-506914

Conventionally, in the hydrotreatment of hydrocarbon oils containing a large amount of metal compounds such as vanadium and nickel, metal compounds such as vanadium and nickel are removed with a demetallation catalyst having high demetallation activity, and then hydrogenation with high desulfurization activity is performed. A method of removing sulfur and nitrogen with a treatment catalyst has been performed. Therefore, even if the conventional demetallation catalyst has a high demetallation activity, the desulfurization activity is low, and the hydrotreating catalyst used in the subsequent stage of the demetallation catalyst has a low demetallation activity even if it has a high desulfurization activity. It was.
An object of the present invention is to use a hydrocarbon oil hydrotreating a high amount of metal compounds such as vanadium and nickel to have a high demetallation activity and a high desulfurization activity. It is an object of the present invention to provide a catalyst composition and a method for hydrotreating a hydrocarbon oil using the catalyst composition.

As a result of intensive studies to achieve the above-mentioned object, the present inventor has found that a catalyst composition in which a manganese compound is present in a fine particle state in a hydroprocessing catalyst composition exhibits high demetallation activity. Nevertheless, the present inventors have found that the desulfurization activity does not decrease and have completed the present invention.
That is, the first aspect of the present invention is a hydrotreating catalyst for hydrocarbon oil, characterized in that the hydrotreating catalyst composition comprising a carrier supporting a hydrotreating metal component contains a particulate manganese compound. Relates to the composition.
The second aspect of the present invention relates to the hydrotreating catalyst composition for hydrocarbon oil according to claim 1, wherein the average particle size of the particulate manganese compound is in the range of 0.5 to 20 μm.
A third aspect of the present invention is the hydrocarbon according to claim 1 or 2, wherein the content of the particulate manganese compound in the hydrotreating catalyst composition is in the range of 0.5 to 60 wt%. The present invention relates to an oil hydrotreating catalyst composition.
A fourth aspect of the present invention relates to the hydrocarbon oil hydrotreating catalyst composition according to any one of claims 1 to 3, wherein the particulate manganese compound is Mn ₂ O ₃ .
According to a fifth aspect of the present invention, the carrier is a porous inorganic oxide selected from alumina, silica-alumina, silica, silica-titania, and silica-zirconia. The hydrocarbon oil hydrotreating catalyst composition described.
According to a sixth aspect of the present invention, the hydrogenation active metal component contains at least one metal component selected from Group VIB metals and Group VIII metals of the Periodic Table. The hydrocarbon oil hydrotreating catalyst composition according to any one of the above.
A seventh aspect of the present invention relates to a hydrocarbon oil hydrotreating method, wherein the hydrotreating catalyst composition according to any one of claims 1 to 6 is used as a catalyst.

The hydrotreating catalyst composition for hydrocarbon oil of the present invention is characterized in that the hydrotreating catalyst composition obtained by supporting a hydrotreating metal component on a carrier contains a particulate manganese compound.
The particulate manganese compound in the present invention means that the manganese compound is not uniformly present in the hydrotreating catalyst composition, but the manganese compound in the particle state is unevenly present. The particulate manganese compound preferably has an average particle size in the range of 0.5 to 20 μm. When the average particle size of the particulate manganese compound is smaller than 0.5 μm, the ability to capture metal compounds such as vanadium and nickel may be weak, and the desired demetalization activity and desulfurization activity cannot be obtained. Sometimes. Moreover, when this average particle diameter is larger than 20 micrometers, the intensity | strength of the hydrotreating catalyst composition obtained may become weak for an industrial catalyst use. The average particle diameter of the particulate manganese compound is more preferably in the range of 1 to 10 μm.
The average particle diameter of the particulate manganese compound in the hydrotreating catalyst composition is determined based on the image of the manganese compound particles from at least five images of the reflected electron images obtained by a scanning electron microscope (SEM; Scanning Electron Microscope). An average value obtained by measuring 500 or more maximum diameters.

  In the hydrotreating catalyst composition of the present invention, the content of the particulate manganese compound is preferably in the range of 0.5 to 60% by weight. If the content is less than 0.5% by weight, the desired demetalization activity may not be obtained. If the content is more than 60% by weight, the desulfurization activity may be reduced. is there. The content of the particulate manganese compound is more preferably in the range of 1 to 40% by weight.

As the particulate manganese compound raw material, any compound that can be transferred to a compound capable of forming a particle state in the hydrotreating catalyst composition can be used. For example, MnO, MnO ₂ , Mn ₂ O ₃ , Mn ₃ O ₄ , MnSO ₄ , MnP, MnSiO ₃ , ZnMn ₂ O ₄ , ZnMn ₂ O ₃ , Zn ₂ MnO ₄ , ZnMn ₃ O ₇ , Zn ₂ Mn ₃ O ₈ , ZnMn (SO ₄ ) ₂ , ZnMn (PO ₄ ) ₂ , Examples include Zn ₂ MnSi ₂ O ₇ , LiZnMn ₃ O ₈ , MnO, MnO ₂ , Mn ₂ O ₃ , Mn ₃ O ₄ , ZnMn ₂ O ₄ , ZnMn ₂ O ₃ , Zn ₂ MnO ₄ , ZnMn ₃ O ₇ Oxides such as Zn ₂ Mn ₃ O ₈ are suitable because they are morphologically stable and relatively inexpensive and easily available in view of industrial production.
The particulate manganese compound is particularly preferably Mn ₂ O ₃ . Since Mn ₂ O ₃ has a particularly strong affinity with vanadium and nickel, these metal compounds are selectively captured by Mn ₂ O ₃ particles, so that poisoning of active sites by metal compounds, and metal compounds Pore clogging due to the deposition of the is difficult to occur. Therefore, the hydrotreating catalyst composition has high demetalization activity without desulfurization activity decreasing.

  In the present invention, a porous inorganic oxide used in a conventional hydroprocessing catalyst composition can be used as a carrier supporting a hydrogenation active component. For example, alumina, silica, titania, zirconia, silica- Examples include alumina, titania-alumina, zirconia-alumina, phosphorus-alumina, boria-alumina, silica-boria-alumina, silica-titania, silica-titania-alumina, silica-zirconia, silica-zirconia-alumina, and the like. In particular, porous inorganic oxides selected from alumina, silica-alumina, silica, silica-titania, and silica-zirconia have good moldability and can easily control physical properties such as pore diameter and pore volume. preferable.

The hydrogenation active metal component in the present invention is at least one metal component selected from Group VIB metal and Group VIII metal of the Periodic Table, and specifically, as Group VIB metal, In particular, molybdenum and tungsten are preferable, and nickel and cobalt are particularly preferable as the Group VIII metal. The hydrogenation active metal component may further contain other components such as phosphorus, if necessary. In particular, the hydrogenation active metal component is preferably a combination of molybdenum and nickel and / or cobalt because of its high desulfurization activity.
The hydrotreating catalyst composition of the present invention comprises 1 to 20% by weight of the Group VIB metal component of the periodic table as an oxide, and 0.5 to 8 of the Group VIII metal component of the periodic table as an oxide. It is preferable to contain in the range of weight%.

  The hydrocarbon oil hydrotreating catalyst composition of the present invention comprises, for example, mixing and kneading the aforementioned porous inorganic oxide precursor and the aforementioned manganese compound particles having a desired average particle diameter in a desired ratio. A kneaded product suitable for extrusion molding is prepared, and the kneaded product is extruded into a desired shape by a usual method, then dried and calcined to prepare a carrier, and the above-mentioned hydrogenation activity is added to the carrier. It is produced by supporting a metal component by an ordinary method. The hydrotreating catalyst composition is prepared by mixing and kneading an aqueous solution containing the aforementioned hydrogenation active metal component together with the aforementioned porous inorganic oxide precursor and the aforementioned manganese compound particles having a desired average particle size. After preparing a kneaded product suitable for extrusion molding, it can be produced by extrusion molding into a desired shape, drying and firing.

The hydrocarbon oil hydrotreating catalyst composition of the present invention has a surface area (SA) of 100 to 350 m ² / g, a pore volume (PV) by mercury intrusion method of 0.40 to 1.10 ml / g, and mercury intrusion. The average pore diameter in the pore distribution measured by the method is desirably in the range of 8 to 30 nm.
The average pore diameter in the pore distribution measured by the mercury intrusion method is 4.2 nm (corresponding to a mercury intrusion pressure of 400 MPa) measured using a contact angle of 150 degrees and a surface tension of 480 dyn / cm. ) The pore diameter corresponding to 1/2 of the above pore volume.
In particular, in the case of a hydrotreating catalyst composition mainly intended for demetalization used in the preceding stage of the hydrotreating reaction tower, the surface area (SA) is preferably 100 to 250 m ² / g, by a mercury intrusion method. The pore volume (PV) is preferably 0.50 to 1.10 ml / g, and the average pore diameter in the pore distribution measured by mercury porosimetry is preferably in the range of 10 to 30 nm.

The hydrocarbon oil hydrotreating catalyst composition of the present invention can be used in an ordinary heavy oil hydrotreating method, and can employ ordinary hydrotreating conditions. For example, the reaction temperature is 300. A range of ˜450 ° C., a hydrogen partial pressure of 5 to 25 MPa, and a liquid space velocity (LHSV) of 0.1 to 5.0 hr ⁻¹ are exemplified.

  The hydrocarbon oil hydrotreating catalyst composition of the present invention contains particulate manganese compounds in the catalyst composition, so that metal compounds such as vanadium and nickel contained in the hydrocarbon oil are subjected to hydrotreating. In addition, it is selectively trapped by the particulate manganese compound and the poisoning of the active site of the catalyst composition by the metal compound such as vanadium or nickel is alleviated. Therefore, the pores of the catalyst composition are hardly blocked. Therefore, the hydrotreating catalyst composition of the present invention is used for heavy oil hydrotreating and has a high demetallizing activity without a decrease in desulfurization activity.

  The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto.

Example 1
Alumina hydrate was prepared using the alumina production apparatus described in the republished WO95 / 15920 related to the present applicant. That is, 719 kg of pure water was put in a tank provided with a circulation line having two chemical solution addition ports, 0.5 kg of a copolymer of isobutylene and maleic anhydride was added thereto, and the mixture was stirred at high speed for about 2 hours to completely dissolve. It was. To this aqueous solution, 2 kg of an aqueous sodium aluminate solution (concentration 22% by weight as Al ₂ O ₃ ) was added with stirring, heated to 60 ° C. and circulated. Next, an aqueous aluminum sulfate solution (concentration 7% by weight as Al ₂ O ₃ ) was added to prepare a seed alumina hydrate slurry. To this slurry, 107.1 kg of sodium aluminate aqueous solution (concentration 22 wt% as Al ₂ O ₃ ) and 168.3 kg of aqueous aluminum sulfate solution (concentration 7 wt% as Al ₂ O ₃ ) were respectively 35.7 kg / hr and 56. With the addition rate of 1 kg / hr, the temperature was kept at 60 ° C. and pH 7.9 to 8.1, and the mixture was added over 3 hours while stirring and circulating to prepare alumina hydrate. The obtained alumina hydrate preparation slurry was washed to obtain an alumina hydrate slurry from which sodium and sulfate radicals were removed. Pure water was added to the alumina hydrate slurry to prepare a slurry with an Al ₂ O ₃ concentration of 10% by weight, and the slurry pH was adjusted to 11 with 15% by weight ammonia water, followed by a reflux. Aging was performed at 95 ° C. for 8 hours in an aging tank. After completion of aging, 30 kg of this slurry ( ₃ kg as Al ₂ O 3) was kneaded while evaporating and concentrating with a double-arm kneader equipped with a steam jacket to obtain a flexible kneaded product (V). To this kneaded product (V), 92.8 g of dimanganese trioxide having an average particle diameter of 0.2 μm (as Mn ₂ O ₃ ) was added, and kneaded with a double-arm kneader for 20 minutes. The alumina kneaded product containing dimanganese trioxide was extruded into an 1.8 mm four-leaf type column by an auger type extruder. The obtained alumina molded article was dried at 110 ° C. for 16 hours, and further calcined at 650 ° C. for 2 hours to obtain an alumina carrier containing 3.0% by weight (based on the carrier) of particulate Mn ₂ O ₃ .
An aqueous phosphoric acid solution of molybdenum trioxide and nickel carbonate is well known so that the support contains molybdenum, nickel, and phosphorus as oxides to 5.9 wt%, 1.45 wt%, and 1.5 wt% based on the catalyst composition. After the impregnation by the above method, the temperature was dried from room temperature to 250 ° C. using a rotary dryer. Further, this dried product was calcined in air at 550 ° C. for 1 hour to prepare Catalyst A.
The maximum diameter of the dimanganese trioxide particles was determined by measuring 100 particles per image from the five images of the reflected electron image of the catalyst A using a scanning electron microscope (SEM). The same applies to the examples) The average particle size was 0.2 μm.
Properties of catalyst A are shown in Table 1.

Example 2
In Example 1, Catalyst B was prepared in the same manner as in Example 1, except that dimanganese trioxide having an average particle size of 0.5 μm was used.
Properties of catalyst B are shown in Table 1.

Example 3
In Example 1, except that dimanganese trioxide having an average particle diameter of 2.1 μm was used and the addition amount of dimanganese trioxide was 15.1 g (as Mn ₂ O ₃ ), Catalyst C was prepared.
The properties of catalyst C are shown in Table 1.

Example 4
A catalyst D was prepared in the same manner as in Example 1 except that dimanganese trioxide having an average particle diameter of 2.1 μm was used in Example 1.
Properties of catalyst D are shown in Table 1.

Example 5
In Example 1, except that manganese monoxide having an average particle diameter of 2.2 μm was used, and the amount of manganese monoxide added was 92.8 g (as Mn ₂ O ₃ ), the same as in Example 1, Catalyst E Was prepared.
Properties of catalyst E are shown in Table 1.

Example 6
In Example 1, Catalyst F was prepared in the same manner as in Example 1, except that dimanganese trioxide having an average particle size of 10.4 μm was used.
Properties of catalyst F are shown in Table 1.

Example 7
In Example 1, except that dimanganese trioxide having an average particle diameter of 2.1 μm was used, and the addition amount of dimanganese trioxide was 333.3 g (as Mn ₂ O ₃ ), the same as in Example 1, Catalyst G was prepared.
Properties of catalyst G are shown in Table 1.

Example 8
In Example 1, except that dimanganese trioxide having an average particle diameter of 2.1 μm was used and the addition amount of dimanganese trioxide was changed to 4500 g (as Mn ₂ O ₃ ), the catalyst H Was prepared.
Properties of catalyst H are shown in Table 1.

Example 9
In Example 1, Catalyst I was prepared in the same manner as Example 1 except that dimanganese trioxide having an average particle size of 20.3 μm was used.
Properties of catalyst I are shown in Table 1.

Example 10
A catalyst J was prepared in the same manner as in Example 1 except that dimanganese trioxide having an average particle size of 23.4 μm was used.
Properties of catalyst J are shown in Table 1.

Example 11
92.8 g of dimanganese trioxide (as Mn ₂ O ₃ ) having an average particle size of 2.1 μm was added to the kneaded material (V) prepared in the same manner as in Example 1, and further molybdenum, nickel and phosphorus were oxidized. As a product, a phosphoric acid aqueous solution of molybdenum trioxide and nickel carbonate was added so as to be 5.9 wt%, 1.45 wt%, and 1.5 wt% on the basis of the catalyst composition, respectively. Kneaded for a minute. The alumina kneaded material containing dimanganese trioxide, molybdenum, nickel and phosphorus was extruded into a 1.8 mm four-leaf type column by an auger type extruder. The obtained alumina molded article was dried at 110 ° C. for 16 hours and then calcined at 680 ° C. for 2 hours to obtain catalyst K.
Properties of catalyst K are shown in Table 1.

Example 12
After aging a silica hydrogel prepared by adding sulfuric acid to water glass, a sodium aluminate aqueous solution and an aluminum sulfate solution are added thereto to prepare a silica alumina hydrate having a SiO ₂ / Al ₂ O ₃ weight ratio of 70/30. did. This silica alumina hydrate slurry was washed to obtain a silica alumina hydrate slurry from which sodium and sulfate radicals had been removed.
30 kg of this slurry ( ₃ kg as SiO ₂ -Al ₂ O 3) was kneaded and evaporated to a flexible kneaded product (W) while evaporating and concentrating with a double-arm kneader with a steam jacket.
To this kneaded product, 92.8 g of dimanganese trioxide having an average particle diameter of 2.1 μm (as Mn ₂ O ₃ ) was added and kneaded for 20 minutes with a double-arm kneader. This silica-alumina kneaded product containing dimanganese trioxide was extruded into an 1.8 mm four-leaf column by an auger type extruder. The obtained silica alumina molded article was dried at 110 ° C. for 16 hours, and further calcined at 680 ° C. for 2 hours to obtain a silica alumina (SiO ₂ —Al ₂ O ₃ ) support containing 3% by weight of manganese particles. .
Molybdenum trioxide and nickel carbonate phosphoric acid with molybdenum, nickel and phosphorus as oxides on the silica-alumina support so as to be 5.9 wt%, 1.45 wt% and 1.5 wt%, respectively, based on the catalyst composition After impregnating with the aqueous solution, it was dried by heating from room temperature to 250 ° C. using a rotary dryer. Further, the obtained dried product was calcined in the air at 550 ° C. for 1 hour to prepare catalyst L.
Properties of the catalyst L are shown in Table 1.

Example 13
A silica hydrogel prepared by adding sulfuric acid to water glass was aged and then washed to obtain a silica hydrate slurry from which sodium and sulfate radicals had been removed.
30 kg of this slurry (3 kg as SiO ₂ ) was kneaded while evaporating and concentrating with a double-arm kneader equipped with a steam jacket, to obtain a plastic kneaded product (X).
To this kneaded product, 92.8 g of dimanganese trioxide having an average particle size of 2.1 μm (as Mn ₂ O ₃ ) was added and kneaded for 20 minutes with a double-arm kneader. This silica kneaded material containing dimanganese trioxide was extruded into an 1.8 mm four-leaf type column by an auger type extruder.
The obtained silica molded article was dried at 110 ° C. for 16 hours, and further fired at 680 ° C. for 2 hours to obtain a silica carrier containing 3% by weight of manganese particles.
An aqueous phosphoric acid solution of molybdenum trioxide and nickel carbonate is added to the silica support so that it becomes 5.9 wt%, 1.45 wt% and 1.5 wt% based on the catalyst composition using molybdenum, nickel and phosphorus as oxides. After impregnation, the temperature was dried from room temperature to 250 ° C. using a rotary dryer.
Furthermore, the obtained dried product was calcined in the air at 550 ° C. for 1 hour to prepare Catalyst M.
The properties of the catalyst M are shown in Table 1.

Example 14
A silica hydrogel prepared by adding sulfuric acid to water glass was aged, and then a titanium sulfate solution was added thereto to prepare silica titania hydrate having a SiO ₂ / TiO ₂ weight ratio of 90/10. The silica titania hydrate slurry was washed to obtain a silica titania hydrate slurry from which sodium and sulfate radicals were removed.
30 kg of this slurry (3 kg as SiO ₂ —TiO ₂ ) was kneaded while evaporating and concentrating with a double-arm kneader with a steam jacket to obtain a plastic kneaded product (Y).
To this kneaded product, 92.8 g of dimanganese trioxide having an average particle size of 2.1 μm (as Mn ₂ O ₃ ) was added and kneaded for 20 minutes with a double-arm kneader. This silica titania kneaded material containing dimanganese trioxide was extruded into an 1.8 mm four-leaf column by an auger type extruder. The obtained silica titania molded article was dried at 110 ° C. for 16 hours, and further fired at 680 ° C. for 2 hours to obtain a silica titania (SiO ₂ —TiO ₂ ) support containing 3% by weight of manganese particles.
An aqueous phosphoric acid solution of molybdenum trioxide and nickel carbonate so that the silica titania carrier has molybdenum, nickel, and phosphorus as oxides to 5.9 wt%, 1.45 wt%, and 1.5 wt% based on the catalyst composition. After being impregnated, it was dried at an elevated temperature from room temperature to 250 ° C. using a rotary dryer. Further, this dried product was calcined in the air at 550 ° C. for 1 hour to prepare catalyst N.
Properties of catalyst N are shown in Table 1.

Example 15
A silica hydrogel prepared by adding sulfuric acid to water glass was aged, and then a zirconium sulfate solution was added thereto to prepare a silica zirconia hydrate having a SiO ₂ / ZrO ₂ weight ratio of 80/20. This silica zirconia hydrate slurry was washed to obtain a silica zirconia hydrate slurry from which sodium and sulfate radicals had been removed.
30 kg of this slurry (3 kg as SiO ₂ —ZrO ₂ ) was kneaded while evaporating and concentrating with a double-arm kneader equipped with a steam jacket to give a plastic kneaded product (Z).
To this kneaded product, 92.8 g of dimanganese trioxide having an average particle size of 2.1 μm (as Mn ₂ O ₃ ) was added and kneaded for 20 minutes with a double-arm kneader. The silica zirconia kneaded material containing dimanganese trioxide was extruded and formed into a 1.8 mm four-leaf column by an auger type extruder. The obtained silica zirconia molded article was dried at 110 ° C. for 16 hours, and further calcined at 680 ° C. for 2 hours to obtain a silica zirconia (SiO ₂ —ZrO ₂ ) support containing 3% by weight of manganese particles.
An aqueous phosphoric acid solution of molybdenum trioxide and nickel carbonate so that the silica zirconia support has 5.9 wt%, 1.45 wt% and 1.5 wt% based on the catalyst composition using molybdenum, nickel and phosphorus as oxides. After being impregnated, it was dried at an elevated temperature from room temperature to 250 ° C. using a rotary dryer. Further, this dried product was calcined in the air at 550 ° C. for 1 hour to prepare Catalyst O.
Properties of catalyst O are shown in Table 1.

Comparative Example 1
The kneaded product (V) prepared in the same manner as in Example 1 was extruded into a 1.8 mm four-leaf type column using an auger type extruder. The obtained alumina molded article was dried at 110 ° C. for 16 hours and then calcined at 680 ° C. for 2 hours to obtain an alumina carrier.
An aqueous phosphoric acid solution of molybdenum trioxide and nickel carbonate is added to the alumina support so that it becomes 5.9 wt%, 1.45 wt% and 1.5 wt% based on the catalyst composition using molybdenum, nickel and phosphorus as oxides. After impregnation, the temperature was dried from room temperature to 250 ° C. using a rotary dryer. Further, this dried product was calcined in the air at 550 ° C. for 1 hour to prepare catalyst P.
Properties of the catalyst P are shown in Table 2.

Comparative Example 2
The kneaded product (V) prepared in the same manner as in Example 1 was extruded into an 1.8 mm four-leaf type column using an auger type extruder. The obtained alumina molded article was dried at 110 ° C. for 16 hours and then calcined at 680 ° C. for 2 hours to obtain an alumina carrier.
To the alumina support, 5.9% by weight, 1.45% by weight, and 1.45% by weight based on the catalyst composition using manganese nitrate, molybdenum, nickel and phosphorus as oxides so as to be 3% by weight as dimanganese trioxide. After impregnating with an aqueous solution of molybdenum trioxide, nickel carbonate and phosphoric acid so as to be 5% by weight, it was dried by heating from room temperature to 250 ° C. using a rotary dryer. Further, this dried product was calcined in the air at 550 ° C. for 1 hour to prepare Catalyst Q.
Properties of catalyst Q are shown in Table 2.

Comparative Example 3
In the same manner as in Example 1, 719 kg of pure water was put into a tank having a circulation line and two chemical addition ports, 0.5 kg of a copolymer of isobutylene and maleic anhydride was added thereto, and the mixture was stirred at high speed for about 2 hours. It was completely dissolved.
To this solution, 2 kg of an aqueous sodium aluminate solution (concentration: 22% by weight as Al ₂ O ₃ ) was added with stirring, heated to 60 ° C. and circulated. Next, an aluminum sulfate solution (7% by weight as Al ₂ O ₃ ) was added to prepare a seed alumina slurry.
To this slurry, 107.1 kg of an aqueous solution of sodium aluminate (concentration 22% by weight as Al ₂ O ₃ ) and 168.3 kg of aluminum sulfate solution (concentration 7% by weight as Al ₂ O ₃ ) were respectively 35.7 kg / hr and 56. It was added over 3 hours at a rate of 1 kg / hr while maintaining a pH of 7.9 to 8.1 at a temperature of 60 ° C. while stirring and circulating. Further, at the same timing, 110.7 kg of an aqueous manganese nitrate solution (1 wt% as Mn ₂ O ₃ ) was added at a rate of 36.9 kg / hr over 3 hours from a chemical solution addition port separately attached to this tank.
This alumina-manganese (Al ₂ O ₃ —Mn ₂ O ₃ ) hydrate preparation slurry was washed to obtain an alumina-manganese hydrate slurry from which sodium, sulfate radicals and nitrate radicals were removed.
Pure water is added to the alumina-manganese hydrate slurry to prepare a slurry having an Al ₂ O ₃ —Mn ₂ O ₃ concentration of 10% by weight, adjusted to pH 11 with 15% by weight ammonia water, It was aged at 95 ° C. for 8 hours in the attached aging tank.
After the ripening, the _{(as Al 2 O 3 + Mn 2 O} 3 3kg) slurry 30kg was kneaded while evaporated by a twin-arm kneader with a steam jacket was kneaded product with a plastic. This alumina-manganese kneaded product was extruded into an 1.8 mm four-leaf type column by an auger type extruder. The obtained alumina-manganese molded article was dried at 110 ° C. for 16 hours, and further calcined at 680 ° C. for 2 hours to be 97 wt% Al ₂ O ₃ -3 wt% Mn ₂ O ₃ support (alumina-manganese support) Got.
Phosphoric acid of molybdenum trioxide and nickel carbonate so that the alumina-manganese support has molybdenum, nickel, and phosphorus as oxides, and becomes 5.9 wt%, 1.45 wt%, and 1.5 wt% based on the catalyst composition. After impregnating with the aqueous solution, it was dried by heating from room temperature to 250 ° C. using a rotary dryer. Further, this dried product was calcined in the air at 550 ° C. for 1 hour to prepare Catalyst R.
Table 2 shows the properties of the catalyst R.

Comparative Example 4
The kneaded product (W) prepared in the same manner as in Example 12 was extruded into a 1.8 mm four-leaf type column with an auger type extruder. The obtained silica alumina molded article was dried at 110 ° C. for 16 hours, and further calcined at 680 ° C. for 2 hours to obtain a silica alumina (SiO ₂ —Al ₂ O ₃ ) support.
To the silica-alumina support, 5.9% by weight, 1.45% by weight, based on the catalyst composition, using manganese nitrate and molybdenum, nickel, and phosphorus as oxides so as to be 3% by weight as dimanganese trioxide. After impregnating with an aqueous solution of molybdenum trioxide, nickel carbonate and phosphoric acid so as to be 1.5% by weight, the mixture was dried at an elevated temperature from room temperature to 250 ° C. using a rotary dryer. Further, this dried product was calcined in the air at 550 ° C. for 1 hour to prepare Catalyst S.
Table 2 shows the properties of the catalyst S.

Comparative Example 5
The kneaded material (X) prepared in the same manner as in Example 13 was extruded into an 1.8 mm four-leaf type column using an auger type extruder. The obtained silica molded article was dried at 110 ° C. for 16 hours, and further calcined at 680 ° C. for 2 hours to obtain a silica carrier.
To the silica support, 5.9% by weight, 1.45% by weight, and 1.45% by weight based on the catalyst composition using manganese nitrate, molybdenum, nickel, and phosphorus as oxides so as to be 3% by weight as dimanganese trioxide. After impregnating with an aqueous solution of molybdenum trioxide, nickel carbonate and phosphoric acid so as to be 5% by weight, it was dried by heating from room temperature to 250 ° C. using a rotary dryer. Further, this dried product was calcined in the air at 550 ° C. for 1 hour to prepare Catalyst T.
Table 2 shows the properties of the catalyst T.

Comparative Example 6
The kneaded product (Y) prepared in the same manner as in Example 14 was extruded into a 1.8 mm four-leaf type column using an auger type extruder. The obtained silica titania molded article was dried at 110 ° C. for 16 hours, and further calcined at 680 ° C. for 2 hours to obtain a silica titania (SiO ₂ —TiO ₂ ) support.
To the silica titania support, 5.9% by weight, 1.45% by weight, based on the catalyst composition, using manganese nitrate and molybdenum, nickel, and phosphorus as oxides so as to be 3% by weight as the support based on dimanganese trioxide, After impregnating with an aqueous solution of molybdenum trioxide, nickel carbonate and phosphoric acid so as to be 1.5% by weight, the mixture was dried at an elevated temperature from room temperature to 250 ° C. using a rotary dryer. Furthermore, this dried product was calcined in the air at 550 ° C. for 1 hour to prepare Catalyst U.
Table 2 shows the properties of the catalyst U.

Comparative Example 7
The kneaded product (Z) prepared in the same manner as in Example 15 was extruded into a 1.8 mm four-leaf type column using an auger type extruder. The obtained molded product of silica zirconia was dried at 110 ° C. for 16 hours, and further calcined at 680 ° C. for 2 hours to obtain a silica zirconia (SiO ₂ —ZrO ₂ ) support.
To the silica zirconia support, 5.9% by weight, 1.45% by weight, based on the catalyst composition, using manganese nitrate and molybdenum, nickel, and phosphorus as oxides so as to be 3% by weight as dimanganese trioxide. After impregnating with an aqueous solution of molybdenum trioxide, nickel carbonate and phosphoric acid so as to be 1.5% by weight, the mixture was dried at an elevated temperature from room temperature to 250 ° C. using a rotary dryer. Further, this dried product was calcined in the air at 550 ° C. for 1 hour to prepare Catalyst V.
Properties of catalyst V are shown in Table 2.

Example 16 Activity Evaluation Test Regarding the catalysts A to O prepared in Examples 1 to 15 and the catalysts P to V prepared in Comparative Examples 1 to 7, the reaction temperature was changed under the following conditions using a fixed bed type microreactor. The activity evaluation test was conducted by changing.
Reaction conditions; catalyst loading 200 ml
Reaction pressure 15 MPa
Liquid space velocity (LHSV) 0.45 hr ⁻¹
Hydrogen / oil ratio (H ₂ / HC) 800 Nm ³ / kl
Reaction temperature 370 ° C, 380 ° C, 390 ° C
Moreover, the normal pressure residual oil of the following property was used for raw material oil.
Raw material oil properties; specific gravity (15/4 ° C.) 0.9831 g / cm ³
Remaining charcoal 11.7% by weight
Asphaltene content 5.2% by weight
Sulfur content 4.236% by weight
Metal (Ni + V) amount 85.3 wt%
The activity was evaluated by passing the feedstock oil under a constant reaction temperature of 380 ° C. under the above reaction conditions, and periodically measuring the amount of metal (Ni + V) in the produced oil and the amount of metal deposited on the catalyst ( When the MOC (Metal on Catalyst) reached 15% by weight, the target reaction temperature was changed to 370, 380, and 390 ° C., and the demetalization rate and desulfurization rate were plotted and drawn against the actual reaction temperature. From the straight line, the demetallation rate and desulfurization rate corresponding to the reaction temperature of 380 ° C. were determined.
The values are shown in Tables 1 and 2.
The demetalization rate and desulfurization rate were determined by the following formulas.
Demetalization rate = {(metal concentration in raw material oil−metal concentration in hydrotreated product oil) / metal concentration in raw material oil} × 100
Desulfurization rate = {(sulfur concentration in feedstock-sulfur concentration in hydrotreated oil) / sulfur concentration in feedstock} × 100
In the examples and comparative examples, the average particle diameter of the raw material manganese compound indicates the value measured by the light transmittance by the sedimentation rate or the sedimentation method.
In Tables 1 and 2, the average particle size (μm) of the manganese compound in the catalyst is a value obtained by measuring the size of the manganese compound particles from the photograph taken with a scanning electron microscope.

From the results of Tables 1 and 2, Catalysts A to K of Examples 1 to 11 in the present invention are catalysts in which particulate manganese compounds are present in the catalyst, and these catalysts do not contain manganese compounds. The catalyst P and manganese compound of Example 1 are not present as particles, and the desulfurization rate and demetalization rate are larger than those of Catalysts Q and R of Comparative Examples 2 and 3, and are excellent in desulfurization activity and demetalization activity. I understand.
Catalyst L shown in Example 12 and Catalyst S shown in Comparative Example 4, Catalyst M shown in Example 13 and Catalyst T shown in Comparative Example 5, Catalyst N shown in Example 14 and Catalyst U shown in Comparative Example 6, Example The catalyst O shown in 15 and the catalyst V shown in Comparative Example 7 have the same carrier component and are compared with those in which the manganese compound is not present as particles. From this result, it can be seen that the catalyst in which manganese compound particles are present as in the previous case has higher desulfurization rate and demetalization value, and is superior in desulfurization activity and demetalization activity.

In Table 1 and Table 2,
(Note) 1) The crushing strength was measured as a pretreatment of 40 or more samples of a length of 4 mm or more from a sample fired at 500 ° C. for 1 hour and cooled with a desiccator to a room temperature. 3.18 mm), and the load when crushed was obtained and calculated by the following formula.
Crushing strength (N / mm) = S × 9.807 / L × n
Here, S is the total pressure load (kg), L is the diameter of the compressor (3.18 mm), and n is the number of measurements.
2) The abrasion strength powdering rate was determined based on ASTM method D 4058-96.
Specifically, as a pretreatment, a sample on a sieve gently sieved with an 850 μm sieve was baked at 500 ° C. for 1 hour, cooled to room temperature with a desiccator, 100 g of the sample was weighed, and ASTM method D 4058-96, put in the drum specified 60 ± 5R. P. Rotated at M speed for 30 minutes. The whole amount of this sample was collected and gently sieved with a 850 μm sieve, the sample on the sieve was baked at 500 ° C. for 1 hour, cooled to room temperature with a desiccator, weighed, and determined by the following formula.
Abrasion strength powdering rate (%) = (W ₀ −W) / W ₀ × 100
Here, W ₀ represents the sample weight (g), and W represents the weight (g) of the baked sample on the 850 μm sieve after the measurement.

Claims (7)

  A hydrotreating catalyst composition for hydrocarbon oil, characterized in that a hydrotreating catalyst composition obtained by supporting a hydrotreating metal component on a carrier contains a particulate manganese compound.   2. The hydrocarbon oil hydrotreating catalyst composition according to claim 1, wherein an average particle size of the particulate manganese compound is in the range of 0.5 to 20 μm.   The hydrotreating catalyst composition for hydrocarbon oil according to claim 1 or 2, wherein the content of the particulate manganese compound in the hydrotreating catalyst composition is in the range of 0.5 to 60 wt%. Stuff. It said particulate manganese compound, hydroprocessing catalyst composition of hydrocarbon oil according to claim 1, characterized in that the Mn ₂ O _3.   The hydrocarbon carrier hydrogen according to any one of claims 1 to 4, wherein the carrier is a porous inorganic oxide selected from alumina, silica-alumina, silica, silica-titania, and silica-zirconia. Catalyst composition.   6. The carbonization according to claim 1, wherein the hydrogenation active metal component contains at least one metal component selected from Group VIB metal and Group VIII metal of the Periodic Table. A hydroprocessing catalyst composition for hydrogen oil. A hydrotreating method for hydrocarbon oil, wherein the hydrotreating catalyst composition according to any one of claims 1 to 6 is used as a catalyst.