KR101158924B1 - Catalyst composition for hydrogenating hydrocarbon oil and hydrotreatment of hydrocarbon oil by using the same - Google Patents

Abstract

[PROBLEMS] Hydrogenated catalyst composition for hydrocarbon oils used in the hydrogenation of hydrocarbon oils containing a large amount of metal compounds such as vanadium and nickel, and having high demetallic activity and high deoiling activity, and hydrocarbons using the catalyst composition It is to provide a significant hydrogenation treatment method.

[Solution] A hydroprocessing catalyst composition for hydrocarbon oil, and a method for hydroprocessing hydrocarbon oil using the catalyst composition, characterized by containing a particulate manganese compound in a hydroprocessing catalyst composition formed by supporting a hydrogenated active metal component on a carrier.

Description

Hydrogenation of Hydrocarbon Oil Catalyst Composition and Hydrogenation Process of Hydrocarbon Oil Using the Catalyst Composition {CATALYST COMPOSITION FOR HYDROGENATING HYDROCARBON OIL AND HYDROTREATMENT OF HYDROCARBON OIL BY USING THE SAME}

The present invention relates to a hydroprocessing catalyst composition of hydrocarbon oil, and more particularly, it is used in the hydroprocessing of hydrocarbon oil containing a large amount of metal compounds such as vanadium and nickel, and exhibits high demetallic activity without degrading deoiling activity. A hydroprocessing catalyst composition of hydrocarbon oil.

Conventional hydroprocessing catalysts are used in industrial applications for the hydrogenation of hydrocarbon oils (hereinafter sometimes referred to as heavy oils) containing a large amount of metal compounds such as vanadium and nickel in the actual apparatus. Occlusion of catalyst pores occurs and deoiling activity and demetallic activity are inactivated, and thus there is a problem that long-term operation cannot be performed.

Further, in oil refineries having a fluid catalytic cracking (FCC) apparatus downstream of the hydrotreatment apparatus, since the product oil obtained by the hydrotreating is used as a raw material for catalytic cracking, the metal compound is removed from the hydrotreatment apparatus. If is not sufficiently performed, a problem that the amount of FCC catalyst used increases because metal compounds such as vanadium and nickel contained in the product oil poison the FCC catalyst and deactivate it. For this reason, when hydroprocessing heavy oil in a hydroprocessing apparatus, the hydroprocessing catalyst composition which performs deoiling and demetalization more effectively was calculated | required.

In response to the above requirements, proposals have been made regarding various hydroprocessing catalyst compositions. For example, Patent Document 1 discloses the use of a catalyst containing an amorphous sulfide with at least one metal selected from the group consisting of iron, Mo, W, and mixtures thereof as a selective hydrogenation denitrification method of a hydrocarbon feedstock. When the catalyst contains at least one metal sulfide of a promoter metal selected from the group consisting of Ni, Co, Zn, Mn, Cu, and mixtures thereof, selective removal of nitrogen from a hydrocarbon feedstock has an excellent effect. Is disclosed.

Patent Document 2 discloses at least one matrix, at least one metal of Group VIIB, and at least Group VIII in the invention of a catalyst containing at least one element of Group VIIB and its use in hydrogenation. at least one metal of group VIB selected from the group consisting of non-noble metals, molybdenum and tungsten, and optionally from at least one element of group VIAA, and from a group consisting of phosphorus, boron and silicon; In addition, a catalyst consisting of additional elements for improving the activity of the catalyst is described, and it is disclosed that at least one metal of group VIIB is preferably rhenium or manganese.

[Patent Document 1] Japanese Patent Application Laid-Open No. 61-162590

[Patent Document 2] Japanese Patent Publication No. 2001-506914

Conventionally, in the hydroprocessing of hydrocarbon oils containing a large amount of metal compounds such as vanadium and nickel, a demetal catalyst having a high demetallic activity is used to remove metal compounds such as vanadium and nickel, followed by a hydrogenation treatment having a high deoiling activity. The method of removing sulfur and nitrogen with a catalyst is performed. For this reason, the conventional demetallurgical catalyst has a low deoiling activity even if the demetallic activity is high, and the dehydrometalization catalyst used at the rear end of the demetallic catalyst has a low demetallic activity even if it has a high deoiling activity.

An object of the present invention is to use for the hydrogenation of hydrocarbon oil containing a large amount of metal compounds such as vanadium, nickel, etc., a hydrogenation catalyst composition of a hydrocarbon oil having a high demetallic activity and a high deoiling activity, and the catalyst composition It is providing the hydrogenation process of the hydrocarbon oil which used this.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to achieve the objective mentioned above, as for the catalyst composition in which the manganese compound exists in particulate form in the hydroprocessing catalyst composition, a deoiling activity does not fall irrespective of showing high demetallic activity. It has come to complete this invention by finding out what is not. That is, the 1st of this invention relates to the hydroprocessing catalyst composition of hydrocarbon oil characterized by containing a particulate manganese compound in the hydroprocessing catalyst composition formed by carrying a hydrogenation active metal component on a support | carrier.

2nd of this invention relates to the hydrogenation catalyst composition of the hydrocarbon oil of Claim 1 in which the average particle diameter of the said particulate manganese compound exists in the range of 0.5-20 micrometers.

The third aspect of the present invention relates to a hydroprocessing catalyst composition of hydrocarbon oil according to claim 1, wherein the content of the particulate manganese compound in the hydroprocessing catalyst composition is in the range of 0.5 to 60% by weight. .

The fourth aspect of the present invention relates to a hydroprocessing catalyst composition of hydrocarbon oil according to any one of claims 1 to 3, wherein the particulate manganese compound is Mn ₂ O ₃ .

The fifth aspect of the present invention is the hydrogenation of the hydrocarbon oil according to any one of claims 1 to 3, wherein the carrier is a porous inorganic oxide selected from alumina, silica-alumina, silica, silica-titania, and silica-zirconia. It relates to a catalyst composition.

A sixth aspect of the present invention is the hydrogenated active metal component according to any one of claims 1 to 3, wherein the hydrogenated active metal component contains at least one metal component selected from Group VIB metals and Group VIII metals of the periodic table. A hydroprocessing catalyst composition of hydrocarbon oil.

A seventh aspect of the present invention relates to a hydroprocessing method of hydrocarbon oil, wherein the hydroprocessing catalyst composition according to any one of claims 1 to 3 is used as a catalyst.

The hydroprocessing catalyst composition of hydrocarbon oil of the present invention is characterized by containing a particulate manganese compound in the hydroprocessing catalyst composition formed by supporting a hydrogenation active metal component on a carrier.

The particulate manganese compound in the present invention means that the manganese compound is not uniformly dispersed in the hydrogenation catalyst composition, but the manganese compound takes a particulate state and is non-uniformly present in the hydrogenation catalyst composition. The particulate manganese compound preferably has an average particle diameter in the range of 0.5 to 20 µm. When the average particle diameter of the said particulate manganese compound is smaller than 0.5 micrometer, the trapping ability of metal compounds, such as vanadium and nickel, may become weak and a desired demetallic activity and deoiling activity may not be obtained. . In addition, when the said average particle diameter is larger than 20 micrometers, the intensity | strength of the obtained hydroprocessing catalyst composition may become weak for industrial catalysts. The average particle diameter of the particulate manganese compound is more preferably in the range of 1 to 10 µm.

In addition, the average particle diameter of the said particulate manganese compound in a hydroprocessing catalyst composition is a particle | grain of a manganese compound from the image of at least 5 places of the reflection electron image by a scanning electron microscope (SEM; Scanning Electron Microscope). This is the average of 500 or more maximum diameters.

In the hydrogenation 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. When the said content is less than 0.5 weight%, a desired demetallic activity may not be obtained, and when the said content is more than 60 weight%, deoiling activity may fall. The content of the particulate manganese compound is more preferably in the range of 1 to 40% by weight.

The particulate manganese compound raw material can be used as long as it is a compound capable of transferring to a compound having a particulate state in the hydroprocessing catalyst composition. For example, MnO, Mn0 ₂ , Mn ₂ 0 ₃ , Mn ₃ 0 ₄ , MnS0 ₄ , MnP, MnSi0 ₃ , ZnMn ₂ 0 ₄ , ZnMn ₂ 0 ₃ , Zn ₂ Mn0 ₄ , ZnMn ₃ 0 ₇ , Zn ₂ Mn ₃ 0 ₈ , ZnMn (SO ₄ ) ₂ , ZnMn (PO ₄ ) ₂ , Zn ₂ MnSi ₂ O ₇ , LiZnMn ₃ 0 _8, and the like are illustrated, and MnO, Mn0 ₂ , Mn ₂ 0 ₃ , Mn ₃ 0 ₄ , ZnMn ₂ 0 ₄ , ZnMn ₂ 0 ₃ , Zn ₂ Mn0 ₄ , ZnMn ₃ 0 ₇ , Zn ₂ Oxides such as Mn ₃ O ₈ are suitable because they are morphologically stable and relatively easy to obtain in consideration of industrial production.

The particulate manganese compound is preferably, particularly in Mn ₂ 0 _3. Since Mn ₂ O ₃ has a particularly high affinity with vanadium and nickel, such metal compounds are selectively trapped in Mn ₂ O ₃ particles, and therefore, poisoning of the active site by metal compounds and deposition of metal compounds Pore blockage is unlikely to occur. For this reason, the hydroprocessing catalyst composition has high demetalization activity without degrading deoiling activity.

In the present invention, as the carrier supporting the hydrogenation active ingredient, a porous inorganic oxide used in a conventional hydroprocessing catalyst composition can be used, for example, alumina, silica, titania, zirconia, silica-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 are exemplified. In particular, porous inorganic oxides selected from alumina, silica-alumina, silica, silica-titania, and silica-zirconia are preferable because they have good moldability and can easily control physical properties such as pore diameter and pore volume.

The hydrogenated active metal component in the present invention is at least one metal component selected from Group VIB metals and Group VIII metals of the periodic table, and specifically, molybdenum and tungsten are particularly preferred as the Group VIB metals. As group VIII metal, nickel and cobalt are especially preferable. The said hydrogenation active metal component may further contain other components, such as phosphorus as needed. In particular, the hydrogenation active metal component is suitable because a combination of molybdenum, nickel and / or cobalt is high in deoiling activity. The hydroprocessing catalyst composition of the present invention contains the group VIB metal component of the periodic table described above as an oxide, and the group VIII metal component of the periodic table as an oxide in the range of 0.5 to 8 wt%. desirable.

The hydroprocessing catalyst composition of the hydrocarbon oil of the present invention comprises, for example, mixing and kneading the precursor of the above-described porous inorganic oxide and the above-described manganese compound particles having a desired average particle diameter in a desired ratio, thereby extruded. A suitable printing material is prepared, and the printing material is extruded into a desired shape by a conventional method, followed by drying and baking to prepare a carrier, and to provide the carrier with the above-mentioned hydrogenated active metal component. It is prepared by supporting in the usual way. In addition, the hydroprocessing catalyst composition is extruded by mixing and kneading an aqueous solution containing the hydrogenated active metal component together with the precursor of the porous inorganic oxide and the manganese compound particles having a desired average particle diameter. It is also possible to prepare a kneading material suitable for the present invention, and then to extrude into a desired shape, to dry it and to produce it.

Hydrogenation catalyst composition of the hydrocarbon oil of the present invention has a surface area (SA) of 100 to 350 m ² / g, a pore volume (PV) of 0.40 to 1.10 ml / g by mercury intrusion, and a pore distribution measured by mercury intrusion. It is preferable that the average pore diameter of is in the range of 8 to 30 nm.

In addition, the average pore diameter in the pore distribution measured by the mercury intrusion method is 1 of the pore volume of 4.2 nm (equivalent to 400 MPa of mercury intrusion pressure) measured by using the contact angle 150 degree and the surface tension of 480 dyn / cm. It is a pore diameter equivalent to / 2.

In particular, in the case of the hydroprocessing catalyst composition mainly intended for demetal used in the front end of the hydroprocessing reaction column, the surface area (SA) is preferably 100 to 250 m ² / g and the pore volume (PV) by mercury intrusion. It is preferable that the average pore diameter in pore distribution measured by this 0.50-1.10 ml / g and mercury porosimetry is in the range of 10-30 nm.

The hydroprocessing catalyst composition of the hydrocarbon oil of the present invention can be used in an ordinary hydrogenation treatment method for heavy oil, and also the usual hydrogenation conditions can be employed, for example, the reaction temperature is in the range of 300 to 450 ° C., hydrogen The partial pressure is in the range of 5 to 25 MPa, and the liquid space velocity (LHSV) is in the range of 0.1 to 5.Ohr ⁻¹ .

[Example]

Although an Example is shown to the following and this invention is demonstrated to it further more concretely, this invention is not limited at all by this.

Example 1

The alumina hydrate was prepared using the manufacturing apparatus of the alumina of Unexamined-Japanese-Patent No. W0 95/15920 which concerns on this applicant. That is, 719 kg of pure water is poured into a tank provided with a circulation line having two chemical liquid addition inlets, and 0.5 kg of a copolymer of isobutylene and maleic anhydride is added thereto, followed by high speed stirring for about 2 hours to completely dissolve it. I was. To this aqueous solution was added 2 kg of an aqueous sodium aluminate solution (a concentration of 22% by weight as Al ₂ O ₃ ) while stirring, and the mixture was heated to 60 ° C and circulated. An aqueous aluminum sulfate solution (concentration 7 wt% as Al ₂ O ₃ ) was then added to prepare a seed alumina hydrate slurry. In this slurry, 107.1 kg of an aqueous sodium aluminate solution (concentration 22% by weight as Al ₂ O ₃ ) and 168.3 kg of an aqueous aluminum sulfate solution (concentration 7% by weight as Al ₂ O ₃ ) were respectively weighed in 35.7 kg / hr and 56.1 kg / hr. The alumina hydrate was prepared by adding for 3 hours, maintaining temperature 60 degreeC and pH 7.9-8.1 at the addition rate, stirring and circulating. The obtained alumina hydrate combination slurry was washed to obtain an alumina hydrate slurry from which sodium and sulfate roots were removed. Pure water was added to this slurry of alumina hydrate to prepare a slurry having an Al ₂ O ₃ concentration of 10% by weight, the slurry pH was adjusted to 11 in 15% by weight ammonia water, and then, at a temperature of 95 ° C in a mating tank equipped with a reflux machine. Time to mature. After completion of aging, 30 kg of this slurry ( ₃ kg as Al ₂ O ₃ ) was triturated while evaporating and condensing with a steam jacket twin kneader to obtain a plasticized vase (V). 92.8 g of dimanganese trioxide (as Mn ₂ O ₃ ) having an average particle diameter of 0.2 μm was added to the kneaded material V, and kneaded for 20 minutes in a twin kneader. The alumina kneading product of the addition of dimanganese trioxide was extruded into a 1.8 mm four-leaf columnar by an auger extruder. The obtained alumina molded product was dried at 110 ° C for 16 hours, and then calcined at 650 ° C for 2 hours to obtain an alumina carrier containing 3.0% by weight of particulate Mn ₂ O ₃ (carrier basis).

The carrier was impregnated with molybdenum trioxide, nickel carbonate, and phosphoric acid aqueous solution so that molybdenum, nickel and phosphorus oxides were 5.9% by weight, 1.45% by weight, and 1.5% by weight based on the catalyst composition. It heated up to 250 degreeC from room temperature. This dried product was further calcined in air at 550 ° C. for 1 hour to prepare catalyst A.

The maximum diameter of dimanganese trioxide particles was measured by measuring 100 pieces of dimanganese trioxide particles from 5 images of reflected electrons by a scanning electron microscope (SEM; Scanning Electron Microscope) of catalyst A. The average particle diameter was 0.2 탆.

The properties of the 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 diameter of 0.5 µm was used.

The properties of Catalyst B are shown in Table 1.

Example 3

In Example 1, using a diantimony manganese having an average particle size of 2.1㎛, and the amount of addition of diantimony manganese to as a, except that in Example 1 with 15.1g (as Mn ₂ 0 _3), to prepare a catalyst C.

The properties of Catalyst C are shown in Table 1.

Example 4

In Example 1, 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.

The properties of Catalyst D are shown in Table 1.

Example 5

In Example 1, using manganese monoxide, having a mean particle size of 2.2㎛, and the addition amount of the manganese monoxide, such as a, except that in Example 1 with 92.8g (as Mn ₂ 0 _3), to prepare a catalyst E.

The properties of Catalyst E are shown in Table 1.

Example 6

In Example 1, catalyst F was prepared like Example 1 except having used dimanganese trioxide of an average particle diameter of 10.4 micrometers.

The properties of Catalyst F are shown in Table 1.

Example 7

For Example 1, using a diantimony manganese having an average particle size of 2.1㎛, and the amount of addition of diantimony manganese to as a, except that in Example 1 with 333.3g (as Mn ₂ 0 _3), to prepare a catalyst G.

The properties of Catalyst G are shown in Table 1.

Example 8

In Example 1, using a diantimony manganese having an average particle size of 2.1㎛, and the amount of addition of diantimony manganese to as a, except that in Example 1 to 4500g (as Mn ₂ 0 _3), to prepare a catalyst H.

The properties of Catalyst H are shown in Table 1.

Example 9

In Example 1, catalyst I was prepared like Example 1 except having used dimanganese trioxide of an average particle diameter of 20.3 micrometers.

The properties of Catalyst I are shown in Table 1.

Example 10

In Example 1, Catalyst J was prepared in the same manner as in Example 1 except that dimanganese trioxide having an average particle diameter of 23.4 μm was used.

The 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 diameter of 2.1 μm was added to the kneaded compound (V) prepared in the same manner as in Example 1, and molybdenum, nickel, and phosphorus were each 5.9 based on the catalyst composition. Molybdenum trioxide, nickel carbonate, and phosphoric acid aqueous solution were added so as to be wt%, 1.45 wt%, and 1.5 wt%, and the mixture was kneaded for 20 minutes in a twin kneader. The alumina prints containing dimanganese trioxide, molybdenum, nickel, and phosphorus were extruded into a 1.8 mm four-leaf columnar with an auger 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 a catalyst K.

The properties of the catalyst K are shown in Table 1.

Example 12

After the silica hydrogel prepared by adding sulfuric acid to the myelin sheath was aged, an aqueous sodium aluminate solution and an aluminum sulfate solution were added thereto to prepare a silica alumina hydrate having a Si0 ₂ / A 1 ₂ 0 ₃ weight ratio of 70/30. The slurry of this silica alumina hydrate was wash | cleaned, and the silica alumina hydrate slurry which removed sodium and sulfate was obtained.

30 kg ( ₃ kg as Si0 ₂ -A1 ₂ 0 ₃ ) of this slurry was concentrated to evaporation with a steam jacketed double kneader to obtain a flammable and plastic foil (W).

92.8 g of dimanganese trioxide (as Mn ₂ O ₃ ) having an average particle diameter of 2.1 μm was added to the kneaded material, and kneaded in a twin kneader for 20 minutes. The silica alumina nitride of this dimanganese trioxide addition was extruded by the Auger type extruder into the four leaf | leaf shape of 1.8 mm. The obtained silica alumina molded product was dried at 110 ° C. for 16 hours, and then calcined at 680 ° C. for 2 hours to obtain a silica alumina (Si0 ₂ -A1 ₂ O ₃ ) carrier containing 3% by weight of manganese particles.

After impregnating the molybdenum trioxide, nickel carbonate and phosphoric acid aqueous solution to the silica alumina carrier to be 5.9% by weight, 1.45% by weight, and 1.5% by weight, respectively, based on the catalyst composition as the oxide of molybdenum, nickel and phosphorus, using a rotary dryer, It heated up to 250 degreeC from room temperature. The resulting dried product was further calcined in air at 550 ° C. for 1 hour to prepare catalyst L.

The properties of the catalyst L are shown in Table 1.

Example 13

Silica hydrogel prepared by adding sulfuric acid to the myelin sheath was aged, and then washed to obtain a silica hydrate slurry from which sodium and sulfate sulfate were removed.

30 kg ( ₃ kg as Si0 ₂ -A1 ₂ O ₃ ) of this slurry was concentrated to evaporation with a steam jacketed double kneader to obtain a flammable and plastic foil (X).

92.8 g of dimanganese trioxide (as Mn ₂ O ₃ ) having an average particle diameter of 2.1 μm was added to the kneaded material, and kneaded in a twin kneader for 20 minutes. Silica kneaded with the addition of dimanganese trioxide was extruded into a 1.8 mm four leaf columnar by Auger type extruder.

The obtained silica alumina molded product was dried at 110 ° C. for 16 hours, and then calcined at 680 ° C. for 2 hours to obtain a silica carrier containing 3% by weight of manganese particles.

The silica carrier was impregnated with molybdenum trioxide, nickel carbonate, and phosphoric acid aqueous solution so as to be 5.9% by weight, 1.45% by weight, and 1.5% by weight based on the catalyst composition as the oxide of molybdenum, nickel, and phosphorus, respectively, and then using a rotary dryer, It heated up to 250 degreeC from and dried.

The obtained dried product was further calcined in air at 550 ° C. for 1 hour to prepare catalyst M.

The properties of the catalyst M are shown in Table 1.

Example 14

After the silica hydrogel prepared by adding sulfuric acid to the myelin sheath was aged, a titanium sulfate solution was added thereto to prepare silica titania hydrate having a Si0 ₂ / Ti 0 ₂ weight ratio of 90/10. The slurry of this silica titania hydrate was washed to obtain a silica titania hydrate slurry from which sodium and sulfate sulfate were removed.

30 kg (3 kg as SiO ₂ -TiO ₂ ) of this slurry was evaporated and concentrated with a steam jacket double kneader to obtain a printing and plasticized printing material (Y).

92.8 g of dimanganese trioxide (as Mn ₂ O ₃ ) having an average particle diameter of 2.1 μm was added to the kneaded material, and kneaded in a twin kneader for 20 minutes. The silica titania printing material of this dimanganese trioxide addition was extruded by the Auger type extruder into the four leaf | leaf shape of 1.8 mm.

The obtained silica titania molded product was dried at 110 ° C. for 16 hours, and then calcined at 680 ° C. for 2 hours to obtain a silica titania (Si0 ₂ -Ti0 ₂ ) carrier containing 3% by weight of manganese particles.

The silica carrier was impregnated with molybdenum trioxide, nickel carbonate, and phosphoric acid aqueous solution so as to be 5.9% by weight, 1.45% by weight, and 1.5% by weight based on the catalyst composition as the oxide of molybdenum, nickel, and phosphorus, respectively, and then using a rotary dryer, It heated up to 250 degreeC from and dried. The resulting dried product was further calcined in air at 550 ° C. for 1 hour to prepare catalyst N.

The properties of catalyst N are shown in Table 1.

Example 15

After the silica hydrogel was prepared by adding sulfuric acid to the myelin sheath, a zirconium sulfate solution was added thereto to prepare a silica zirconia hydrate having a Si0 ₂ / Zr0 ₂ weight ratio of 80/20. The slurry of this silica zirconia hydrate was wash | cleaned, and the silica zirconia hydrate slurry from which sodium and sulfate were removed was obtained.

30 kg (3 kg as SiO ₂ -Zr0 ₂ ) of this slurry was evaporated and concentrated by a steam jacketed double kneader to obtain a flammable and plasticized nitride (Z).

92.8 g of dimanganese trioxide (as Mn ₂ O ₃ ) having an average particle diameter of 2.1 μm was added to the kneaded material, and kneaded in a twin kneader for 20 minutes. The silica zirconia kneading of this dimanganese trioxide addition was extruded by the Auger type | mold extruder into the four-lobed columnar shape of 1.8 mm.

The obtained silica zirconia molded article was dried at 110 ° C. for 16 hours, and then calcined at 680 ° C. for 2 hours to obtain a silica zirconia (Si0 ₂ -Zr0 ₂ ) carrier containing 3% by weight of manganese particles.

After impregnating the molybdenum trioxide, nickel carbonate and phosphoric acid aqueous solution to the silica zirconia carrier so that the molybdenum, nickel and phosphorus oxides were 5.9% by weight, 1.45% by weight, and 1.5% by weight based on the catalyst composition, respectively, and then using a rotary dryer. It heated up to 250 degreeC from room temperature. The resulting dried product was further calcined in air at 550 ° C. for 1 hour to prepare catalyst O.

The properties of the catalyst O are shown in Table 1.

Comparative Example 1

The raw material (V) prepared in the same manner as in Example 1 was extruded into a four-lobed columnar of 1.8 mm with an Auger 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.

The alumina carrier was impregnated with molybdenum trioxide, nickel carbonate and phosphoric acid aqueous solution so that molybdenum, nickel and phosphorus oxides were 5.9% by weight, 1.45% by weight, and 1.5% by weight, respectively, based on the catalyst composition. It heated up to 250 degreeC from and dried. The obtained dried product was further calcined in air at 550 ° C. for 1 hour to prepare catalyst P.

The properties of the catalyst P are shown in Table 2.

Comparative Example 2

The raw material (V) prepared in the same manner as in Example 1 was extruded into a four-lobed column of 1.8 mm using an Auger 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.

Manganese acetate, and molybdenum, nickel and phosphorus as oxides of 5.9% by weight, 1.45% by weight, and 1.5% by weight, based on the catalyst composition, as the manganese trioxide, as the manganese trioxide in the alumina carrier. After impregnating the aqueous phosphoric acid solution, the temperature was dried from room temperature to 250 ° C. using a tumble dryer. The resulting dried product was further calcined in air at 550 ° C. for 1 hour to prepare catalyst Q.

The properties of the catalyst Q are shown in Table 2.

Comparative Example 3

In the same manner as in Example 1, 719 kg of pure water was injected into a tank having a circulation line and two chemical liquid addition inlets, and 0.5 kg of a copolymer of isobutylene and maleic anhydride was added thereto, followed by stirring at high speed for about 2 hours. Completely dissolved.

Sodium aluminate solution were added with stirring to 2kg (concentration 22% by weight as Al ₂ 0 ₃₎ to the solution, and was circulated by heating to 60 ℃. Then, an aluminum sulfate solution (concentration 7 wt% as Al ₂ O ₃ ) was added to prepare a seed alumina hydrate slurry.

In this slurry, 107.1 kg of an aqueous sodium aluminate solution (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 charged at 35.7 kg / hr and 56.1 kg / hr, respectively. At the rate of addition, under the temperature of 60 ° C., pH was maintained at 7.9 to 8.1 and added for 3 hours while stirring and circulating. At the same timing, 110.7 kg of an aqueous solution of manganese acetate (1% by weight as Mn ₂ O ₃ ) was added at a rate of 36.9 kg / hr for 3 hours from the chemical liquid addition port provided separately in this tank.

The alumina-manganese (Al ₂ O ₃ -Mn ₂ O ₃ ) hydrate combination slurry was washed to obtain an alumina-manganese hydrate slurry from which sodium, sulfate and acetate were removed.

Pure water was added to this slurry of alumina-manganese hydrate to prepare a slurry having an Al ₂ 0 ₃ -Mn ₂ 0 ₃ concentration of 10% by weight, and the slurry pH was adjusted to 11 with 15% by weight of ammonia water, and then a reflux device was attached. It matured at 95 degreeC in the aging tank for 8 hours.

After completion of aging, 30 kg of this slurry ( ₃ kg as Al ₂ O ₃ + Mn ₂ O ₃ ) was triturated while evaporating and condensing with a steam jacketed twin kneader to obtain a plastic foil. The alumina-manganese kneaded material was extruded into a 1.8 mm four leaf columnar by Auger extruder. The resulting alumina-manganese molded product was dried at 110 ° C. for 16 hours, and then calcined at 650 ° C. for 2 hours to obtain 97% by weight Al ₂ O ₃ -3% by weight Mn ₂ 0 ₃ carrier (alumina-manganese carrier).

Molybdenum trioxide, nickel carbonate and phosphoric acid aqueous solution were impregnated into the alumina-manganese carrier such that molybdenum, nickel and phosphorus were 5.9% by weight, 1.45% by weight, and 1.5% by weight based on the catalyst composition, and then using a rotary dryer. It heated up and dried from room temperature to 250 degreeC. This dried product was further calcined in air at 550 ° C. for 1 hour to prepare catalyst R.

The properties of the catalyst R are shown in Table 2.

Comparative Example 4

The raw material (W) prepared in the same manner as in Example 12 was extruded into a four-lobed column of 1.8 mm by Auger extruder. The obtained silica alumina molded product was dried at 110 ° C. for 16 hours, and then calcined at 680 ° C. for 2 hours to obtain a silica alumina (Si0 ₂ -Al ₂ O ₃ ) carrier.

To the silica alumina carrier, manganese acetate, and molybdenum, nickel, and phosphorus are 5.9% by weight, 1.45% by weight, and 1.5% by weight of molybdenum trioxide and carbonic acid based on the catalyst composition as oxides of manganese trioxide to 3% by weight based on the carrier. After impregnating the aqueous solution of nickel and phosphoric acid, it heated up and dried from room temperature to 250 degreeC using the rotary dryer. This dried product was further calcined in air at 550 ° C. for 1 hour to prepare catalyst S.

The properties of the catalyst S are shown in Table 2.

Comparative Example 5

The raw material (X) prepared in the same manner as in Example 13 was extruded into a four-lobed column of 1.8 mm with an Auger extruder. The obtained silica molded article was dried at 110 ° C. for 16 hours, and then calcined at 680 ° C. for 2 hours to obtain a silica carrier.

To the silica carrier, manganese acetate to 3% by weight based on the carrier as dimanganese trioxide, and molybdenum trioxide and carbonic acid to 5.9% by weight, 1.45% by weight and 1.5% by weight based on the catalyst composition as oxides of molybdenum, nickel and phosphorus After impregnating the aqueous solution of nickel and phosphoric acid, it heated up and dried from room temperature to 250 degreeC using the rotary dryer. This dried product was further calcined in air at 550 ° C. for 1 hour to prepare catalyst T.

The properties of the catalyst T are shown in Table 2.

Comparative Example 6

The raw material (Y) prepared in the same manner as in Example 14 was extruded into a four-lobed columnar of 1.8 mm by an auger extruder. The obtained silica titanium dioxide molded product was dried at 110 ° C for 16 hours, and then calcined at 680 ° C for 2 hours to obtain a silica titanium dioxide (Si0 ₂ -TiO ₂ ) carrier.

To the silica titanium dioxide carrier, manganese acetate to 3% by weight based on the carrier as manganese trioxide, and molybdenum and nickel and phosphorus oxides to 5.9% by weight, 1.45% by weight, and 1.5% by weight based on the catalyst composition; After impregnating the aqueous solution of nickel carbonate and phosphoric acid, the temperature was dried from room temperature to 250 ° C. using a tumble dryer. This dried product was further calcined in air at 550 ° C. for 1 hour to prepare catalyst U.

The properties of the catalyst U are shown in Table 2.

Comparative Example 7

The raw material (Z) prepared in the same manner as in Example 15 was extruded into a 1.8 mm four-leaf columnar with an auger extruder. The obtained silica zirconia molded article was dried at 110 ° C. for 16 hours, and then calcined at 680 ° C. for 2 hours to obtain a silica zirconia (Si0 ₂ -ZrO ₂ ) carrier.

To the silica zirconia carrier, manganese acetate, and molybdenum, nickel and phosphorus are 5.9% by weight, 1.45% by weight, and 1.5% by weight of molybdenum trioxide and carbonic acid, based on the catalyst composition as oxides of manganese trioxide to 3% by weight based on the carrier. After impregnating the aqueous solution of nickel and phosphoric acid, it heated up and dried from room temperature to 250 degreeC using the rotary dryer. This dried product was further calcined in air at 550 ° C. for 1 hour to prepare catalyst V.

The properties of Catalyst V are shown in Table 2.

Example 16

Activity evaluation test

About catalysts A-O prepared in Examples 1-15 and catalysts P-V prepared in Comparative Examples 1-7, reaction temperature was changed on the conditions shown next using the micro-reactor of fixed common sense, Activity evaluation test was done.

Reaction conditions; Catalyst Charge 200ml

           Reaction pressure 15MPa

Liquid Space Velocity (LHSV) 0.45hr ^-l

Hydrogen / Ubi (H ₂ / HC) 800Nm ³ / kl

                 Reaction temperature 370 ℃, 380 ℃, 390 ℃

In addition, the atmospheric residual oil of the following characteristics was used for raw material oil.

Crude oil properties; Specific gravity (15/4 ℃) 0.9831 g / cm ³

             Xanthan 11.7% by weight

             Aspartene powder 5.2% by weight

             Sulfur content 4.236 wt%

             Metal (Ni + V) content 85.3ppm

In the activity evaluation, the crude metal was constantly passed through the raw material oil at the reaction temperature of 380 ° C. under the above reaction conditions, and the metal deposited on the catalyst was measured from the amount of metal (Ni + V) and the oil flow rate in the product oil regularly measured. When the amount (MOC: Metal on Catayst) reached 15% by weight, the target reaction temperature was changed to 370 ° C., 380 ° C., and 390 ° C. to react, and the demetallization rate and deoiling rate were floated with respect to the actual reaction temperature. From the straight line, the demetallization rate and deoiling rate corresponding to the reaction temperature of 380 ° C were determined.

The values are shown in Table 1 and Table 2.

In addition, the demetalization rate and deoiling rate were calculated | required by the following formula.

Demetallization ratio = {(Metal Concentration in Raw Oil-Metal Concentration in Hydrogenated Production Oil) / Metal Concentration in Raw Oil} × 100

Deoiling rate = {(sulfur concentration in raw oil-sulfur concentration in hydroprocessed produced oil) / sulfur concentration in raw oil} × 100

In an Example and a comparative example, the average particle diameter of the manganese compound of a raw material shows the value measured by the light transmittance by the sedimentation velocity, or the sedimentation method.

In Table 1 and 2, the average particle diameter (micrometer) of the manganese compound in a catalyst took the photograph with the scanning electron microscope the cross section with a catalyst, and shows the value which measured the size of the particle | grains of the manganese compound from a photograph. .

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 a particulate manganese compound is present in the catalyst, and this catalyst does not contain a manganese compound. It can be seen that the values of the deoiling rate and the demetallic rate are greater than those of the catalysts Q and R of Comparative Examples 2 and 3 in which the catalyst P and the manganese compound are not present as particles, and the deoiling activity and the demetallic activity are excellent.

Catalyst L shown in Example 12, Catalyst S shown in Comparative Example 4, Catalyst M shown in Example 13, 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 each compare the same carrier component and do not assume that a manganese compound exists as particles. From this result, as mentioned above, it turns out that the catalyst in which the manganese compound particle exists is large in the value of a deoiling rate and a demetallic rate, and excellent in a deoiling activity and a demetallic activity.

Table 1

Table 2

In Table 1 and Table 2,

(Note) 1) The crushing strength is that which calcined the sample at 500 ° C for 1 hour as a pretreatment.

After cooling by a desiccator, 40 or more samples having a length of 4 mm or more are compressed using a wood hardness tester (compressor 3.18 mm), and the load when crushed is obtained. Calculated.

Crush Strength (N / mm) = S × 9.807 / (L × n)

Here, S denotes the total pressure load (kg), L denotes the diameter of the compressor (3.18 mm), and n denotes the number of measurements.

2) The wear strength differentiation rate was calculated | required based on ASTM method D4058-96.

Specifically, after preliminarily sintering the sample of the sifted body carefully at 500 ° C. for 1 hour with a 850 μm sieve as a pretreatment, the sample was cooled to a room temperature and weighed by 100 g of the sample therefrom, followed by the ASTM method. It was put in the drum prescribed by D4058-96, and it rotated for 30 minutes at the speed of 60 +/- 5 R.PM. The whole amount of this sample was collect | recovered, it carefully screened by the 850 micrometers sieve, and the sample on the said body was baked at 500 degreeC for 1 hour, cooled in room temperature to a desiccator, this was weighed, and it calculated | required by following Formula.

Wear Strength Differentiation Rate (%) = (Wo-W) / Wo × 100

Here, Wo represents the sample weight (g), and W represents the weight (g) of the fired sample on the 850 µm body after the measurement.

In the hydroprocessing catalyst composition of the hydrocarbon oil of the present invention, since a particulate manganese compound is present in the catalyst composition, metal compounds such as vanadium and nickel contained in the hydrocarbon oil are selectively trapped by the particulate manganese compound during the hydrogenation treatment, Since poisoning of the active site of the catalyst composition by metal compounds such as vanadium and nickel is alleviated, and furthermore, the deposition of metal compounds on the surface of the catalyst composition is reduced, the pore blocking of the catalyst composition is unlikely to occur. For this reason, the hydroprocessing catalyst composition of this invention is used for the hydroprocessing of heavy oil, and has high demetallic activity, without deoiling activity falling.

Claims (7)

MnO, Mn0 ₂ , Mn ₂ 0 ₃ , Mn ₃ 0 ₄ , MnS0 ₄ , MnP in particulate form having an average particle diameter in the range of 0.5 to 20 μm in a hydroprocessing catalyst composition formed by supporting a hydrogenated active metal component on a support , MnSi0 ₃ , ZnMn ₂ 0 ₄ , ZnMn ₂ 0 ₃ , Zn ₂ Mn0 ₄ , ZnMn ₃ 0 ₇ , Zn ₂ Mn ₃ 0 ₈ , ZnMn (SO ₄ ) ₂ , ZnMn (PO ₄ ) ₂ , Zn ₂ MnSi ₂ O ₇ , LiZnMn ₃ 0 ₈ at least one manganese compound in the range of 0.5 to 60% by weight of hydrogenated hydrogenated catalyst composition characterized in that it contains. The catalyst composition for hydroprocessing heavy hydrocarbon oil according to claim 1, wherein the carrier is a porous inorganic oxide selected from alumina, silica-alumina, silica, silica-titania, and silica-zirconia. 3. The hydroprocessing catalyst composition of heavy hydrocarbon oil according to claim 1 or 2, wherein the hydrogenation active metal component contains at least one metal component selected from Group VIB metals and Group VIII metals of the periodic table. A hydrogenation treatment method for heavy hydrocarbon oil, comprising using the hydroprocessing catalyst composition according to claim 1 as a catalyst. delete delete delete