WO2021193617A1

WO2021193617A1 - Hydroprocessing catalyst for heavy hydrocarbon oil, method for producing hydroprocessing catalyst for heavy hydrocarbon oil, and method for hydroprocessing heavy hydrocarbon oil

Info

Publication number: WO2021193617A1
Application number: PCT/JP2021/011956
Authority: WO
Inventors: 山田　晃; 中嶋　伸昌
Original assignee: コスモ石油株式会社
Priority date: 2020-03-26
Filing date: 2021-03-23
Publication date: 2021-09-30
Also published as: JPWO2021193617A1

Abstract

The present invention relates to a hydroprocessing catalyst for a heavy hydrocarbon oil, the hydroprocessing catalyst comprising phosphorus- and zinc-containing alumina that serves as a support and at least one metal selected from group-6 metals on the periodic table and cobalt both supported on the support, in which the phosphorus- and zinc-containing alumina contains phosphorus in an amount of 0.1 to 4% by mass in terms of oxide content relative to the amount of the support and also contains zinc in an amount of 1 to 8% by mass in terms of oxide content relative to the amount of the support, the at least one metal is supported on the support in an amount of 8 to 30% by mass in terms of oxide content relative to the amount of the catalyst, and cobalt is supported on the support in an amount of 2 to 8% by mass in terms of oxide content relative to the amount of the catalyst.

Description

A method for producing a hydrogenation treatment catalyst for heavy hydrocarbon oil, a method for producing a hydrogenation treatment catalyst for heavy hydrocarbon oil, and a method for hydrogenation treatment of heavy hydrocarbon oil.

The present invention relates to a method for producing a hydrogenation treatment catalyst for heavy hydrocarbon oil, a method for producing a hydrogenation treatment catalyst for heavy hydrocarbon oil, and a method for hydrogenation treatment of heavy hydrocarbon oil.
The present application claims priority based on Japanese Patent Application No. 2020-056301 filed in Japan on March 26, 2020, the contents of which are incorporated herein by reference.

Each oil fraction obtained by distillation or decomposition of crude oil generally contains sulfur compounds, and when these oils are used as fuel, sulfur oxides and the like caused by these sulfur compounds are generated. Therefore, in the process of producing petroleum products from crude oil, a hydrogenation treatment process for removing sulfur compounds is provided.

The sulfur compound is also present in a high concentration in the reduced pressure light oil, which is a distillate obtained by further reducing the pressure distilled residual oil obtained by treating the crude oil with the atmospheric distillation apparatus with the vacuum distillation apparatus. Therefore, the reduced pressure gas oil is hydrogenated by an indirect desulfurization apparatus.

In order to improve the efficiency of hydrogenation treatment by the indirect desulfurization equipment, hydrogenation treatment catalysts are being developed. As a hydrogenation treatment catalyst, a catalyst has been developed in which a metal of Group 6 of the periodic table and cobalt are active species, and these active species are supported on an inorganic oxide carrier containing alumina as a main component.

Patent Document 1 discloses a hydrogenation catalyst for reduced pressure gas oil containing molybdenum, cobalt, and phosphorus. When the state of alumina constituting the carrier in the hydrogenation treatment catalyst ^{is analyzed using 27} Al-NMR, the ratio of the area strength attributed to the tetracoordinated Al to the coordinating structure of the Al atom is the total. It is disclosed that the hydrotreating activity is improved when the amount is 30% or more and the outer surface area of the catalyst is 3500 mm ^{2 / ml or more.}

Japanese Unexamined Patent Publication No. 2004-74075

In recent years, there has been an increasing demand for bottomless oil, and after hydrogenating heavy hydrocarbon oil, it is processed with a fluid cracking device to produce intermediate distillates such as gasoline, kerosene and light oil. Since it is necessary to reduce the sulfur content of the raw material oil supplied to the fluid cracking apparatus to a certain level or less from the viewpoint of protecting the fluid cracking catalyst, hydrodesulfurized heavy hydrocarbon oil should be hydrogenated. Is required. Therefore, there is a demand for a hydrogenation treatment catalyst in which the hydrogenation treatment activity of the heavy hydrocarbon oil is high and the activity is hard to decrease. However, the hydrogenation treatment activity and the catalyst life of the hydrogenation treatment catalyst described in Patent Document 1 are not sufficient.

INDUSTRIAL APPLICABILITY The present invention has been made in view of the above circumstances, and is a hydrogenation treatment catalyst for heavy hydrocarbon oil, which has high hydrogen treatment activity for heavy hydrocarbon oil and whose activity does not easily decrease. It is an object of the present invention to provide a method for producing a hydrogenation treatment catalyst for hydrogen oil and a method for hydrogenation treatment of heavy hydrocarbon oil using the hydrogenation treatment catalyst for heavy hydrocarbon oil.

As a result of diligent studies to achieve the above object, the present inventors used a phosphorus / zinc-containing alumina containing a specific amount of phosphorus and zinc as a carrier, and used the phosphorus / zinc-containing alumina carrier as a metal of Group 6 of the periodic table. By using at least one selected from the above and a hydrogenation treatment catalyst of a heavy hydrocarbon oil carrying a specific amount of cobalt, the hydrogenation treatment activity of the heavy hydrocarbon oil is high and the activity is less likely to decrease. We found that and completed the present invention.

That is, the present invention relates to the following hydrogenation treatment catalyst for heavy hydrocarbon oil, a method for producing a hydrogenation treatment catalyst for heavy hydrocarbon oil, and a method for hydrogenation treatment of heavy hydrocarbon oil.
[1] A phosphorus / zinc-containing alumina containing 0.1 to 4% by mass of phosphorus on a carrier basis and 0.1 to 4% by mass on an oxide basis as a carrier, and zinc containing 1 to 8% by mass on a carrier basis as a carrier.
Heavy hydrocarbons on which at least one selected from Group 6 metals of the Periodic Table is supported on the carrier based on a catalyst, 8 to 30% by mass in terms of oxide, and cobalt is supported on a catalyst standard, 2 to 8% by mass in terms of oxide. Oil hydrogenation catalyst.
[2] The periodic table No. 6 is added to a phosphorus-zinc-containing alumina carrier containing 0.1 to 4% by mass of phosphorus on a carrier basis and 0.1 to 8% by mass on an oxide basis, and zinc containing 1 to 8% by mass on a carrier basis. A heavy hydrocarbon having a step of supporting at least one selected from group metals so as to contain at least one selected from the group metals so as to contain 8 to 30% by mass in terms of oxides and 2 to 8% by mass in terms of oxides based on catalysts. A method for producing an oil hydrogenation catalyst.
[3] The heavy hydrocarbon according to [1], with a hydrogen / oil ratio of 100 to 1000 Nm ³ / kL, a hydrogen partial pressure of 3.5 to 10 MPa, 330 to 430 ° C., and a liquid space velocity of 0.2 to 2 hr ^-1. A method for producing a hydrotreated heavy hydrocarbon oil, which comprises contact-treating an oil hydrotreated catalyst and a heavy hydrocarbon oil.
[4] The heavy hydrocarbon according to [1], with a hydrogen / oil ratio of 100 to 1000 Nm ³ / kL, a hydrogen partial pressure of 3.5 to 10 MPa, 330 to 430 ° C., and a liquid space velocity of 0.2 to 2 hr ^-1. A method for hydrogenating a heavy hydrocarbon oil, which comprises contact-treating an oil hydrogenating catalyst and a heavy hydrocarbon oil.

According to the present invention, it is possible to provide a hydrogenation treatment catalyst for a heavy hydrocarbon oil, which has a high hydrogenation treatment activity of the heavy hydrocarbon oil and the activity does not easily decrease. Further, it is possible to provide a method for producing a hydrogenation treatment catalyst for the heavy hydrocarbon oil and a method for hydrogenating the heavy hydrocarbon oil using the hydrogenation treatment catalyst for the heavy hydrocarbon oil.

Hereinafter, embodiments of the present invention will be described in detail, but the following description is an example of embodiments of the present invention, and the present invention is not limited to these contents, and is modified and implemented within the scope of the gist thereof. can do.

<Hydrogenation catalyst for heavy hydrocarbon oil>
The hydrogenation treatment catalyst of the heavy hydrocarbon oil of the present embodiment (hereinafter, may be simply referred to as “hydrolysis treatment catalyst”) contains phosphorus in an amount of 0.1 to 4% by mass in terms of an oxide based on a carrier. Using zinc as a carrier standard and phosphorus / zinc-containing alumina containing 1 to 8% by mass in terms of oxide as a carrier, at least one selected from Group 6 metals of the periodic table is used as the carrier based on a catalyst and 8 to 8 to 8 to 8 in terms of oxide. 30% by mass, cobalt is supported on a catalyst basis, and 2 to 8% by mass in terms of oxide.
In the present specification, the "group 6 metal of the periodic table" (hereinafter, may be referred to as "metal of group 6") means the metal of group 6 in the long-periodic table.
In the present specification, Group 6 metals and cobalt are collectively referred to as "hydrogenation active ingredients".

A phosphorus-zinc-containing alumina carrier containing phosphorus and zinc will be described.
The main component of the carrier of the hydrogenation catalyst of this embodiment is alumina. As the alumina, various aluminas such as α-alumina, β-alumina, γ-alumina, and δ-alumina can be used. Alumina, which is porous and has a high specific surface area, is preferable, and γ-alumina is more preferable.
The purity of alumina is preferably 98% by mass or more, more preferably 99% by mass or more.
The impurities in the _{^{^{_{alumina, SO 4 2-, Cl -,}}}} Fe 2 O 3, Na 2 O , and the like. It is preferable that these impurities are as small as possible. The content of the total amount of impurities with respect to the total mass of alumina is preferably 2% by mass or less, and more preferably 1% by mass or less.
In each component, based on the total weight of alumina, _SO ^{4 2-1.5} wt% or ^{_{_{less, Cl -, Fe 2 O 3}}} , Na 2 O is preferably is 0.1 wt% or less, respectively.

The alumina used as the carrier of the hydrogenation treatment catalyst of the present embodiment may be composite alumina in which at least one oxide selected from zeolite, boria, silica, and zirconia is composited. Composite alumina means a mixture or composite oxide of alumina and at least one oxide selected from zeolite, boria, silica, and zirconia.
The content of alumina is preferably 92 to 99.9% by mass, more preferably 95 to 98% by mass, based on the total mass of the composite alumina. The content of at least one oxide selected from zeolite, boria, silica, and zirconia with respect to the total mass of the composite alumina is preferably 0.1 to 8% by mass, more preferably 2 to 5% by mass. As the above-mentioned zeolite, boria, silica, and zirconia as the composite component, those generally used as a carrier component of this type of catalyst can be used.

The carrier of the hydrogenation treatment catalyst of the present embodiment is a phosphorus-zinc-containing alumina carrier in which phosphorus and zinc are further contained in an alumina carrier (including a composite alumina carrier).
Phosphorus and zinc are added as components for improving the quality of active points in order to improve the hydrogenation treatment activity and the de-residual coal activity per amount of the hydrogenation active component. Phosphorus and zinc play a role in precisely creating a hydrogenation active ingredient-sulfur phase such as a highly active CoMoS phase and CoWS phase. Further, the inclusion of phosphorus and zinc suppresses a decrease in the activity of the hydrogenation catalyst.

The content of zinc in the carrier of the hydrogenation treatment catalyst of the present embodiment is 1 to 8% by mass, preferably 1 to 6% by mass, and more preferably 1 to 5% by mass in terms of carrier standard and oxide. More preferably, it is 1% by mass or more and less than 4% by mass. When the zinc content is at least the lower limit of the above range, the sulfurization degree of the Group 6 metal can be sufficiently improved. In addition, the decrease in activity of the hydrogenation catalyst is suppressed. When the zinc content is not more than the upper limit of the above range, the pore volume and the specific surface area are unlikely to decrease, the Group 6 metal is sufficiently dispersed, and the cobalt sulfide degree is unlikely to decrease.

The content of phosphorus in the carrier of the hydrogenation treatment catalyst of the present embodiment is 0.1 to 4% by mass, preferably 0.5 to 2% by mass, in terms of the carrier standard and oxides. When the phosphorus content is at least the lower limit of the above range, the sulfurization degree of the Group 6 metal can be sufficiently improved. In addition, a decrease in the activity of the hydrogenation catalyst is suppressed. When the phosphorus content is not more than the upper limit of the above range, the pore volume and the specific surface area are unlikely to decrease, and the Group 6 metal is sufficiently dispersed, so that the effect of adding phosphorus can be sufficiently obtained.

In the present specification, with respect to the contents of phosphorus and zinc, "carrier standard, in terms of oxide" means that the masses of all the elements contained in the carrier are calculated as the respective oxides, and the total mass of phosphorus relative to the total mass thereof is calculated. It means the oxide mass and the ratio of the zinc oxide mass. The oxide mass of phosphorus _{is converted to diphosphorus pentoxide (P 2} O ₅ ), and the oxide mass of zinc is converted to zinc oxide (Zn O).
In the present specification, the mass of the element contained in the carrier or the hydrogenation treatment catalyst can be measured by inductively coupled plasma emission spectrometry.

It is considered that the hydrogenation catalyst of the present embodiment contains phosphorus and zinc to alleviate the interaction of the carrier with the Group 6 metal and cobalt, and facilitates the sulfurization of the Group 6 metal and cobalt, respectively. .. On the other hand, if the interaction between the Group 6 metal or cobalt and the carrier becomes too weak, the hydrogenation active ingredient will aggregate, so precise control is required for the addition of phosphorus and zinc. In the hydrogenation treatment catalyst of the present embodiment, by precisely controlling and adding phosphorus and zinc, the number of layers is maintained while maintaining a state in which the hydrogenation active component-sulfur phase such as CoMoS phase and CoWS phase is highly dispersed. It is considered that the structural form such as is also optimized.

The phosphorus / zinc-containing alumina carrier of the hydrogenation treatment catalyst of the present embodiment preferably has the following physical property values.

The specific surface area of the phosphorus-zinc-containing alumina support, as the value measured by a nitrogen adsorption method (BET method), preferably from 200 ~ 400m ² / g, more preferably 250 ~ 360m ² / g. When the specific surface area is not more than the lower limit of the above range, the hydrogenation active ingredient is sufficiently dispersed, so that the hydrogenation treatment activity becomes high. When the specific surface area is not more than the upper limit of the above range, the carrier has a sufficiently large pore diameter, so that the pore diameter of the hydrogenation treatment catalyst is also sufficiently large. Therefore, the sulfur compound is sufficiently diffused into the catalyst pores, and the hydrogenation treatment activity is enhanced. That is, when the specific surface area is within the above range, a hydrogenation treatment catalyst having good dispersibility of the hydrogenation active ingredient and having a sufficiently large pore diameter can be obtained.

The average pore diameter in the pore distribution measured by the mercury intrusion method of the phosphorus / zinc-containing alumina carrier is preferably 4 to 12 nm, more preferably 6 to 8 nm. When the average pore diameter is within the above range, the surface area in the pores is sufficient, the sulfur compound is sufficiently diffused into the catalyst pores, and the hydrogenation treatment activity is increased.

The pore volume of the phosphorus / zinc-containing alumina carrier is preferably 0.5 to 0.9 mL / g, more preferably 0.55 to 0.8 mL / g, as measured by the mercury intrusion method. When the pore volume is at least the lower limit of the above range, the amount of solvent that enters the pores becomes sufficient when the catalyst is prepared by a usual impregnation method. When the amount of the solvent is sufficient, the hydrogenation active component dissolves well in the solvent, the dispersibility of the hydrogenation active component is improved, and the catalyst becomes a highly active catalyst. There is a method of adding a large amount of an acid such as nitric acid in order to increase the solubility of the hydrogenation active component, but if it is added too much, the surface area of the carrier will be reduced, which will be the main cause of the decrease in the hydrogenation treatment activity. When the pore volume is not more than the upper limit of the above range, the specific surface area becomes sufficiently large and the dispersibility of the hydrogenation active ingredient is improved. That is, when the pore volume is within the above range, it has a sufficient specific surface area and a sufficient amount of solvent can enter the pore volume, so that both the solubility and dispersibility of the hydrogenation active component are good. Therefore, the hydrogenation treatment activity is further improved.

The hydrogenation treatment catalyst of the present embodiment is a catalyst in which a Group 6 metal and cobalt are supported as hydrogenation active components on the phosphorus / zinc-containing alumina carrier.

The content of zinc in the hydrogenation treatment catalyst of the present embodiment is preferably 0.5 to 7% by mass, more preferably 0.7 to 6.5% by mass, and 1 to 6% by mass in terms of catalyst standard and oxide. % Is more preferable. When the zinc content is at least the lower limit of the above range, the sulfurization degree of the Group 6 metal can be sufficiently improved. In addition, a decrease in the activity of the hydrogenation catalyst is suppressed. When the zinc content is not more than the upper limit of the above range, the pore volume and the specific surface area are unlikely to decrease, the Group 6 metal is sufficiently dispersed, and the cobalt sulfide degree is unlikely to decrease.

The content of phosphorus in the hydrogenation treatment catalyst of the present embodiment is preferably 0.5 to 8% by mass, more preferably 0.5 to 4.5% by mass, in terms of oxides based on the catalyst, and 3.6% by mass. It is more preferably more than% and 4.5% by mass or less. When the phosphorus content is at least the lower limit of the above range, the sulfurization degree of the Group 6 metal can be sufficiently improved. In addition, a decrease in the activity of the hydrogenation catalyst is suppressed. When the phosphorus content is not more than the upper limit of the above range, the pore volume and the specific surface area are unlikely to decrease, and the Group 6 metal is sufficiently dispersed, so that the effect of adding phosphorus can be sufficiently obtained.

In the present specification, with respect to the contents of phosphorus and zinc, "catalyst standard, in terms of oxide" means that the masses of all the elements contained in the catalyst are calculated as the respective oxides, and the total mass of phosphorus is calculated. It means the oxide mass and the ratio of the zinc oxide mass. The oxide mass of phosphorus _{is converted to diphosphorus pentoxide (P 2} O ₅ ), and the oxide mass of zinc is converted to zinc oxide (Zn O).

Examples of the Group 6 metal include molybdenum (Mo), tungsten (W), chromium (Cr) and the like, and among them, molybdenum having a high hydrogenation treatment activity per unit mass is preferable.
Further, only one type of Group 6 metal may be supported, or two or more types may be used in combination.
The amount of the Group 6 metal supported on the phosphorus / zinc-containing alumina carrier is 8 to 30% by mass, preferably 10 to 25% by mass, in terms of catalyst standard and oxide. When the amount of the Group 6 metal supported is equal to or greater than the lower limit of the above range, it is sufficient to exhibit the effect caused by the Group 6 metal. When the amount of the Group 6 metal supported is not more than the upper limit of the above range, the Group 6 metal is difficult to aggregate and is sufficiently dispersed. That is, since the amount of the Group 6 metal that can be efficiently dispersed is not exceeded and the surface area of the catalyst is not significantly reduced, the catalytic activity can be improved.

The amount of cobalt supported on the phosphorus / zinc-containing alumina carrier is 2 to 8% by mass, preferably 2.5 to 5% by mass, in terms of catalyst standard and oxide. When the amount of cobalt supported is at least the lower limit of the above range, active sites attributable to cobalt can be sufficiently obtained. When the amount of cobalt supported is not more than the upper limit of the above range, cobalt is less likely to aggregate and is sufficiently dispersed.

The hydrogenation treatment reaction includes a desulfurization reaction, a hydrogenation reaction other than the desulfurization reaction, and the like. When a hydrogenation treatment reaction is carried out in a reactor having a low hydrogen partial pressure for the main purpose of a desulfurization reaction, when a hydrogenation reaction other than the desulfurization reaction proceeds, hydrogen in the reactor is consumed and coking is likely to occur. Since the hydrogenation treatment catalyst of the present embodiment contains cobalt, it is possible to suppress hydrogenation reactions other than the desulfurization reaction and suppress the occurrence of coking. As a result, the decrease in activity of the hydrogenation catalyst over time is suppressed.

Here, regarding the amount of the Group 6 metal and cobalt carried, "catalyst standard, in terms of oxide" means that the masses of all the elements contained in the catalyst are calculated as the respective oxides, and the total mass thereof is calculated. It means the ratio of the oxide mass of each metal. The oxide mass of the Group 6 metal and cobalt is determined by converting the Group 6 metal into a hexavalent oxide (for example, MoO _{3 in the} case of Mo) and the cobalt by converting it into a divalent oxide (CoO).

In terms of the amount of each component of Group 6 metal and cobalt, the optimum mass ratio of Group 6 metal and cobalt, which are hydroactive components, is [Cobalt oxide mass] / [Cobalt oxide mass + No. 1 The value of the oxide mass of the Group 6 metal] is preferably 0.14 to 0.3.
When the ratio of the mass of the cobalt oxide to the total mass of the group 6 metal oxide and the cobalt oxide is equal to or higher than the lower limit of the above range, the CoMoS phase and CoWS considered to be the active points of the hydrogenation treatment reaction. The hydrogenation active component of the same phase-sulfur phase is sufficiently generated, and the hydrogenation treatment activity is increased. When the ratio of the mass of the cobalt oxide to the total mass of the group 6 metal oxide and the cobalt oxide is not more than the upper limit of the above range, the metal species (CoS species and CoS species) that are not involved in the hydrotreating activity Co spinel species incorporated into the lattice of the carrier) is less likely to be generated, and the hydrotreating activity is increased.

The hydrogenation catalyst may contain impurities such as _{SO 4} ^2- , Cl ⁻ , Fe ₂ O ₃ and Na ₂ O derived from alumina contained in the carrier. These impurities are preferably as small as possible, and the content ratio of the total amount of impurities to the total mass of the hydrogenation treatment catalyst is preferably 2% by mass or less, and more preferably 1% by mass or less. In each _component, ^{SO 4 2-1.5} wt% or ^{_{_{less, Cl -, Fe 2 O 3}}} , Na 2 O is preferably is 0.1 wt% or less, respectively.

The hydrogenation treatment catalyst of the present embodiment preferably has the following physical property values in order to enhance the hydrogenation treatment activity for heavy hydrocarbon oil.

The specific surface area of the hydrotreating catalyst of the present embodiment is a value measured by the BET method, preferably 150 ~ 300m ² / g, more preferably 190 ~ 250m ² / g. When the specific surface area is not more than the lower limit of the above range, the hydrogenation active ingredient is sufficiently dispersed, so that the hydrogenation treatment activity becomes high. When the specific surface area is not more than the upper limit of the above range, the hydrogenation catalyst has a sufficiently large pore diameter.
Therefore, the sulfur compound is sufficiently diffused into the catalyst pores, and the hydrogenation treatment activity is enhanced. That is, when the specific surface area is within the above range, both the dispersibility of the hydrogenation active component and the diffusibility of the sulfur compound into the catalyst pores during the hydrogenation treatment can be improved.

The average pore diameter in the pore distribution measured by the mercury intrusion method of the hydrogenation treatment catalyst of the present embodiment is preferably 5 to 20 nm, more preferably 7 to 11 nm. When the average pore diameter is within the above range, the diffusibility of the sulfur compound into the catalyst pores is enhanced while having a sufficient surface area in the pores (that is, the effective surface area of the catalyst), and the hydrogenation treatment activity is further enhanced. Can be improved.

The pore volume of the hydrogenation catalyst of the present embodiment is preferably 0.45 to 0.8 mL / g, more preferably 0.45 to 0.7 mL / g, as measured by the mercury intrusion method. When the pore volume is at least the lower limit of the above range, the sulfur compound diffuses sufficiently in the catalyst pores during the hydrogenation treatment, and the hydrogenation treatment activity is improved. When the pore volume is not more than the upper limit of the above range, it is possible to prevent the specific surface area of the catalyst from becoming extremely small. When the pore volume is within the above range, both the dispersibility of the hydrogenation active ingredient and the diffusibility of the sulfur compound into the catalyst pores during the hydrogenation treatment can be improved.

In order to increase the effective number of pores satisfying the above average pore diameter and pore volume, the pore diameter distribution of the hydrogenation catalyst of the present embodiment is as follows: average pore diameter ± 1. The volume ratio of the pores having a pore diameter of 5 nm is preferably 65% or more, more preferably 70% or more.

Further, the distribution state of the hydrogenation active ingredient in the hydrogenation treatment catalyst of the present embodiment is preferably a uniform type in which the hydrogenation active ingredient is uniformly distributed in the catalyst.

<Manufacturing method of hydrogenation catalyst for heavy hydrocarbon oil>
In the method for producing a hydrogenation treatment catalyst for heavy hydrocarbon oil of the present embodiment, phosphorus is contained in a carrier standard and 0.1 to 4% by mass in terms of oxide, and zinc is contained in a carrier standard and 1 to 8 in terms of oxide. In a phosphorus / zinc-containing alumina carrier containing mass%, at least one selected from Group 6 metals in the periodic table is used as a catalyst standard, 8 to 30% by mass in terms of oxide, and cobalt is used as a catalyst standard, and 2 to 8 in terms of oxide. It has a step of supporting it so as to contain it in mass%.

The phosphorus / zinc-containing alumina carrier contains, for example, a step of preparing an alumina gel, phosphorus in a carrier standard, 0.1 to 4% by mass in terms of oxide, zinc in a carrier standard, and 1 to 8% by mass in terms of oxide. It has a step of adding a phosphorus compound and a zinc compound to the alumina gel and kneading the mixture, and a step of molding the obtained kneaded product and drying and firing the obtained molded product.

In order to obtain the phosphorus-zinc-containing alumina carrier used for the hydrogenation treatment catalyst of the present embodiment, first, an alumina gel is obtained by a conventional method.
As the alumina raw material, any substance containing aluminum can be used, but aluminum salts such as aluminum sulfate and aluminum nitrate are preferable. These alumina raw materials are usually provided as an aqueous solution, and the concentration thereof is not particularly limited, but is preferably 2 to 50% by mass, more preferably 5 to 40% by mass, based on the total mass of the aqueous solution.

As for the preparation of alumina gel, for example, first, a sulfuric acid aqueous solution, sodium aluminate, and aluminum hydroxide are mixed in a stirring pot to prepare a slurry. The obtained slurry is subjected to water removal and pure water washing with a rotary cylindrical continuous vacuum filter to obtain an alumina gel.

Then, the resulting alumina gel SO 4 _2-in the ^filtrate, washing until Na ⁺ can not be detected, a uniform slurry by turbid the alumina gel in pure water. The obtained alumina gel slurry is dehydrated until the water content with respect to the total mass of the slurry becomes 60 to 90% by mass to obtain a cake.

In the production method of the present embodiment, it is preferable that the alumina gel slurry is dehydrated by a squeezing filter. The squeeze filter is a device that filters the slurry by applying compressed air or pump pressure, and is also generally called a squeeze filter. There are two types of squeezing filters: plate frame type and intaglio type. In the plate frame type pressure filter, the filter plate and the filter frame are alternately tightened between the end plates, and the slurry is press-fitted into the filter frame to filter. The filter plate has a groove that serves as a flow path for the filtrate, and the filter frame is covered with a filter cloth. On the other hand, in the intaglio type pressure filter, the filter cloth and the intaglio type filter plate are alternately arranged to form a tightening filter chamber between the end plate (reference: Chemical Engineering Handbook p715).

As described above, in the production method of the present embodiment, the water content at the time of preparing the alumina used as the carrier is adjusted by the above-mentioned squeezing filter. By dehydrating with a squeeze filter, the surface condition of the alumina carrier can be improved, and the degree of sulfurization of the hydrogenation active ingredient can be improved. The dehydration step using the squeeze filter is preferably performed after at least one of the steps of preparing the above alumina gel and the step of kneading the phosphorus compound and the zinc compound described later, and after both steps. You may go. Above all, it is more preferable to carry out after preparing the alumina gel and before kneading the phosphorus compound and the zinc compound.

In addition to the above methods, as a method for preparing an alumina gel, a method of neutralizing an aqueous solution containing an alumina raw material with a neutralizing agent such as sodium aluminate, aluminate, or ammonia, or a precipitating agent such as hexanemethylenetetramine or calcium carbonate. A method of mixing with and the like can be mentioned.
The amount of the neutralizing agent used is not particularly limited, but is preferably 30 to 70% by mass with respect to the total amount of the aqueous solution containing the alumina raw material and the neutralizing agent. The amount of the precipitant used is not particularly limited, but is preferably 30 to 70% by mass with respect to the total amount of the aqueous solution containing the alumina raw material and the precipitant.

When a composite alumina obtained by compounding an oxide such as zeolite is used as a carrier for a hydrogenation treatment catalyst, first, an alumina gel is prepared by a conventional method, and the obtained alumina gel is aged, washed, and dehydrated. This may be done after drying and adjusting the water content, and before adding the phosphorus compound and zinc. As a compounding method, alumina can be composited with an oxide such as zeolite by a coprecipitation method, a kneading method or the like. The composite alumina gel is aged, washed, dehydrated and dried, and the moisture content is adjusted. Also in the final dehydration step before molding the composite alumina gel, it is preferable to dehydrate using a squeeze filter.

Various compounds can be used as the zinc compound to be added to the carrier of the hydrogenation treatment catalyst of the present embodiment, and zinc oxide, zinc nitrate, zinc sulfate, zinc carbonate, zinc chloride, zinc acetate, and zinc hydroxide , Zinc oxalate and the like are given as examples, and among them, zinc oxide, zinc nitrate and zinc sulfate are preferable, and zinc oxide is particularly preferable.

Various compounds can be used as the phosphorus compound added to the carrier of the hydrogenation treatment catalyst of the present embodiment. Examples of the phosphorus compound include orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid and the like, and orthophosphoric acid is preferable.

A phosphorus compound and a zinc compound are added to the alumina gel obtained above by kneading. Specifically, a phosphorus compound and a zinc compound heated to 15 to 90 ° C. are added to a moisture-adjusted product of an alumina gel heated to 50 to 90 ° C. Then, the mixture is kneaded and stirred using a heating kneader or the like to obtain a kneaded product of an alumina gel, a phosphorus compound and a zinc compound. As described above, dehydration by a squeeze filter may be performed after kneading and stirring the alumina gel with the phosphorus compound and the zinc compound. The phosphorus compound may be added directly, or a phosphorus solution (or suspension) in which the phosphorus compound is dissolved (or suspended) in a solvent may be added.

Then, the obtained kneaded product is molded, dried, and fired to obtain a phosphorus / zinc-containing alumina carrier. The kneaded product can be molded by various molding methods such as extrusion molding and pressure molding. The drying temperature for drying the obtained molded product is preferably 15 to 150 ° C, more preferably 80 to 120 ° C. The drying time is preferably 30 minutes or more. The firing temperature of the firing can be appropriately set as needed, but for example, in order to obtain γ-alumina, the firing temperature is preferably 450 ° C. or higher, more preferably 480 to 600 ° C. The firing time is preferably 2 hours or more, more preferably 3 to 12 hours.

The method of adding the zinc compound and the phosphorus compound does not depend on the above kneading method, and the zinc compound and the phosphorus compound may be supported on the alumina carrier by a method other than kneading. As a method for supporting the zinc compound and the phosphorus compound on the alumina carrier by a method other than kneading, known methods such as an impregnation method, a coprecipitation method, a deposition method, and an ion exchange method may be used. The impregnation method includes an evaporative drying method in which the components are supported by immersing the alumina carrier in an impregnated solution in excess of the total pore volume of the alumina carrier and then drying all the solvent, and the alumina carrier is the alumina carrier. Equilibrium adsorption method for obtaining a catalyst in which components are supported by solid-liquid separation such as filtration after immersion in an impregnated solution that is excessive with respect to the total pore volume of the alumina carrier. An example is a pore filling method in which a component is supported by impregnating the impregnated solution of (1) and drying all the solvent. The method for impregnating the alumina carrier with the zinc compound and the phosphorus compound may be a one-stage impregnation method in which each of these components is impregnated at the same time, or a two-stage impregnation method in which the alumina carrier is individually impregnated.

When a zinc compound or a phosphorus compound is supported by the above impregnation method or the like, the moisture content is generally 50% or less at room temperature to 80 ° C. in a nitrogen stream, an air stream, or a vacuum. It is removed and dried in an air stream at 80 to 150 ° C. for 10 minutes to 10 hours in a drying oven. Then, in a firing furnace, firing is performed at 300 to 700 ° C., more preferably 500 to 650 ° C. for 10 minutes to 10 hours, more preferably 3 hours to 6 hours in an air stream.

As for the support of the zinc compound and the phosphorus compound on the alumina carrier, the entire amount may be supported by the kneading method, or a part of the zinc compound and the phosphorus compound may be supported by the kneading method and the rest may be supported by the impregnation method or the like. However, the entire amount may be supported by the impregnation method or the like.

The phosphorus / zinc-containing alumina carrier thus obtained is subsequently supported with a Group 6 metal and cobalt.

In the hydrogenation treatment catalyst of the present embodiment, the raw material compound of the Group 6 metal to be supported on the phosphorus / zinc-containing alumina carrier is preferably a molybdenum compound, and molybdenum trioxide, molybdenic acid, ammonium molybdate, molybdate, and the like are preferable. Molybdolic acid, molybdenum trioxide, and ammonium molybdate are preferred.

In the hydrogenation treatment catalyst of the present embodiment, examples of the cobalt raw material compound supported on the phosphorus / zinc-containing alumina carrier include cobalt carbonate, cobalt acetate, cobalt nitrate, cobalt sulfate, cobalt chloride, and the like, and cobalt carbonate and acetic acid. Cobalt is preferred, and cobalt carbonate is more preferred.

As a method for supporting the Group 6 metal or cobalt on the phosphorus / zinc-containing alumina carrier, a known method such as an impregnation method, a coprecipitation method, a kneading method, a deposition method, or an ion exchange method may be used. As an impregnation method, the hydrogenation active component is supported by immersing the phosphorus / zinc-containing alumina carrier in an impregnation solution excessively equal to the total pore volume of the phosphorus / zinc-containing alumina carrier and then drying all the solvent. The hydroactive component was supported by solid-liquid separation such as filtration after immersing the phosphorus-zinc-containing alumina carrier in the impregnation solution in excess of the total pore volume of the phosphorus-zinc-containing alumina carrier by the evaporation-dry solid method. In the equilibrium adsorption method for obtaining a catalyst, the phosphorus / zinc-containing alumina carrier is impregnated with an impregnated solution in an amount substantially equal to the total pore volume of the phosphorus / zinc-containing alumina carrier, and the solvent is completely dried to obtain the hydrogenation active component. An example is a supported pore filling method. The method of impregnating the phosphorus / zinc-containing alumina carrier with the group 6 metal raw material compound and the cobalt raw material compound may be a one-step impregnation method in which each of these components is impregnated at the same time, or a two-step impregnation method in which the phosphorus / zinc-containing alumina carrier is individually impregnated. ..

Specific methods for supporting the Group 6 metal, cobalt, on a phosphorus / zinc-containing alumina carrier include the following methods.
An impregnating solution containing a raw material compound of a Group 6 metal and a raw material compound of cobalt is prepared. At the time of preparation, in order to promote the dissolution of these compounds, heating (30 to 100 ° C.) and addition of acids (nitrate, phosphoric acid, organic acids << citric acid, acetic acid, malic acid, tartaric acid, etc. >>) are performed. You may. That is, in the present embodiment, in addition to the phosphorus contained in the phosphorus-zinc-alumina carrier, when the Group 6 metal or cobalt is supported on the phosphorus-zinc-alumina carrier, phosphorus may be separately supported.

Phosphorus compounds to be added separately when carrying the Group 6 metal, cobalt on a phosphorus-zinc-alumina carrier include phosphorus-containing raw material compounds for hydrogenation active components such as molybdric acid, orthophosphoric acid, metaphosphoric acid, and pyrophosphoric acid. , Triphosphoric acid, tetraphosphoric acid, and orthophosphoric acid is preferable. When the Group 6 metal, cobalt, is supported on the phosphorus-zinc alumina carrier, if phosphorus is separately supported, the dispersibility of the hydrogenation active component can be improved.

Subsequently, the prepared impregnation solution is gradually added to the phosphorus / zinc-containing alumina carrier so as to be uniform and impregnated. The impregnation time is preferably 1 minute to 5 hours, more preferably 5 minutes to 3 hours. The impregnation temperature is preferably 5 to 100 ° C, preferably 10 to 80 ° C. The impregnation atmosphere is not particularly limited, but air, nitrogen, and vacuum are suitable.

The ratio of the oxide-equivalent mass of phosphorus kneaded in the carrier to the oxide-equivalent mass of the Group 6 metal is preferably 0.25 or less. When it is 0.25 or less, the surface area and pore volume of the catalyst are not reduced, the decrease in catalytic activity is suppressed, and carbon precipitation can be prevented without increasing the amount of acid, which causes deterioration of activity. It is suppressed.

When molybdenum is used as the Group 6 metal, the ratio of the oxide-equivalent mass of phosphorus kneaded in the carrier to the oxide-equivalent mass of molybdenum is preferably 0.01 to 1.5, preferably 0.05 to 1. 0 is more preferable. When the ratio of the oxide-equivalent mass of phosphorus kneaded in the carrier to the oxide-equivalent mass of molybdenum is within the above range, the cobalt and molybdenum can be completely integrated.

In the method for producing a hydrogenation catalyst of the present embodiment, after supporting a raw material compound of a Group 6 metal and a raw material compound of cobalt, the impregnated material is first placed in a nitrogen stream, an air stream, or a vacuum at 15 to 80 ° C. Remove some water (so that LOI << Loss on ignition >> is 50% or less). Then, it is dried in an air stream at 80 to 150 ° C. for 10 minutes to 10 hours in a drying oven. Next, firing is performed in an air stream in a firing furnace. The firing temperature is preferably 300 to 700 ° C, more preferably 500 to 650 ° C. The firing temperature is preferably 10 minutes to 10 hours, more preferably 3 hours or more.

The phosphorus contained in the hydrogenation treatment catalyst of the present embodiment is a _{group consisting of the phosphorus compound, phosphorus oxide (P 2} O ₅ ) produced by the firing, phosphorus, aluminum, zinc, Group 6 metal, and cobalt. Examples include composite oxides with at least one element selected from the above.

The zinc contained in the hydrogenation treatment catalyst of the present embodiment is selected from the group consisting of the zinc compound, zinc oxide (ZnO) produced by the firing, zinc, aluminum, phosphorus, Group 6 metal, and cobalt. Examples include composite oxides with at least one element.

Examples of the Group 6 metal contained in the hydrogenation treatment catalyst of the present embodiment include the raw material compound of the Group 6 metal, the oxide produced by the firing (specific example: MoO ₃ ), the Group 6 metal, and aluminum. An example is a composite oxide with at least one element selected from the group consisting of zinc, phosphorus and cobalt.

The cobalt contained in the hydrogenation treatment catalyst of the present embodiment includes the raw material compound of cobalt, an oxide produced by the firing (specific example: CoO), cobalt, aluminum, zinc, phosphorus, and a Group 6 metal. An example is a composite oxide with at least one element selected from the group.

The hydrogenation catalyst of the present embodiment prepared as described above preferably has a Group 6 metal sulfide degree of 84 mol% or more, which is represented by the following formula, and is 86 mol%. The above is more preferable.
Group 6 metal sulfurization = [(M6 (IV) / M6) x 100]
[In the above formula, M6 (IV) is the molar amount of Group 6 metal sulfide in the sulfided catalyst, and M6 is the molar amount of all Group 6 metal elements in the sulfided catalyst].
Here, the group 6 metal sulfide degree of the XPS quantitative analysis result is the ratio (molar ratio) of the amount of group 6 metal sulfide (M6 (IV)) in the sulfided catalyst to the total amount of group 6 metal elements (M6). ) Means.
For example, when molybdenum is used as the Group 6 metal used in this catalyst, the molybdenum sulfide degree [(Mo (IV) / Mo) × 100] of the XPS quantitative analysis result is the amount of molybdenum disulfide (molar amount) in the sulfided catalyst. ) Means the ratio (molybdenum ratio) to the total amount of molybdenum. The molybdenum sulfide degree is preferably 84 mol% or more, and more preferably 86 mol% or more.
Further, Group 6 metal sulfide amount in catalyst sulfide (molar amount), the catalyst of the present invention, the content of H _{2 S} to the total volume of the mixed gas (mixed gas of H 2 _S and H ₂ is 4.8 Volume%) Under 50 ml / min circulation, the temperature is raised at 5 ° C./min, treated at 300 ° C. for 10 minutes to sulfide, then purged with high-purity helium gas for 10 min, and XPS measurement is performed in vacuum exhaust. Obtainable.

Further, in the catalyst of the present invention, the cobalt sulfide degree of the XPS quantitative analysis result represented by the following formula is preferably 60 mol% or more, more preferably 65 mol% or more.
Cobalt sulfide = [(cobalt sulfide amount / cobalt element amount) x 100]
Here, the cobalt sulfide degree of the XPS quantitative analysis result means the ratio (molar ratio) of the cobalt sulfide amount (molar amount) to the cobalt element amount (molar amount) in the sulfided catalyst.
That is, the cobalt sulfide degree [(CoS / Co) × 100] of the XPS quantitative analysis result means the ratio (molar ratio) of the amount of cobalt monosulfide in the sulfided catalyst to the total amount of cobalt. The cobalt sulfurization degree is preferably 60 mol% or more, and more preferably 65 mol% or more.

<Hydrogenated heavy hydrocarbon oil production method (hydrocarbonated heavy hydrocarbon oil)>
The method for producing the hydrogenated heavy hydrocarbon oil of the present embodiment is a water / oil ratio of 100 to 1000 Nm ³ / kL, a hydrogen partial pressure of 3.5 to 10 MPa, a reaction temperature of 330 to 430 ° C., and a liquid space velocity (hereinafter referred to as). ^{Under the condition of 0.2 to 2 hr -1} (also referred to as LHSV), the hydrogenation treatment catalyst of the present invention and a heavy hydrocarbon oil containing a sulfur compound are contact-treated to carry out hydrogenation treatment, and the heavy hydrogenation is carried out. Reduces the sulfur content in the oil to produce hydrogenated heavy hydrocarbon oil.
The method for hydrogenating the heavy hydrocarbon oil of the present embodiment is a water / oil ratio of 100 to 1000 Nm ³ / kL, a hydrogen partial pressure of 3.5 to 10 MPa, a reaction temperature of 330 to 430 ° C., and a liquid space velocity of 0.2 to. A method for hydrogenating a heavy hydrocarbon oil, which comprises contacting the hydrogenation catalyst of the present invention with a heavy hydrocarbon oil containing a sulfur compound in 2hr- ^1.

Hydrogen / oil ratio is preferably 100 ~ 1000 Nm ³ / kL, and more preferably from 175 ~ 925Nm ³ / kL, still more preferably 250 ~ 850Nm ³ / kL. The hydrogen partial pressure is preferably 3.5 to 10 MPa, more preferably 4 to 9 MPa. When the hydrogen partial pressure is equal to or higher than the lower limit of the above range, the hydrogenation reaction tends to proceed.
The reaction temperature is preferably 330 to 430 ° C, more preferably 350 to 410 ° C. When the reaction temperature is at least the lower limit of the above range, the catalytic activity can be sufficiently exhibited. When the reaction temperature is not more than the upper limit of the above range, the thermal decomposition of the heavy hydrocarbon oil proceeds moderately, but the catalyst deterioration is unlikely to occur.
The reaction temperature means the average temperature of the catalyst bed.
The LHSV is preferably 0.2 to 2 hr ^-1 , and more preferably 0.5 to 2 hr ^-1 .

As the heavy hydrocarbon oil used in the method for producing a hydrocarbon-treated heavy hydrocarbon oil of the present embodiment (method for hydrogenating a heavy hydrocarbon oil), crude oil is distilled under atmospheric pressure with an atmospheric distillation apparatus. Lubricating oil base oil such as vacuum light oil obtained by further vacuum distillation of the obtained atmospheric distillation residual oil with a vacuum distillation apparatus, atmospheric heavy oil obtained by atmospheric distillation of crude oil with a vacuum distillation apparatus, hydrocarbon cracked heavy oil, etc. Among the oils extracted and removed by solvent extraction, heavy extract, atmospheric distillation residual oil, fluidized catalytic decomposition residual oil, thermal decomposition heavy oil, gravel oil, etc., which are particularly heavy oils, are vacuum-reduced light oils. , Heavy extract, fluidized catalytic decomposition residual oil, thermal decomposition heavy oil are preferable, and vacuum light oil is particularly preferable.
The hydrogenation treatment catalyst of hydrocarbon oil contains a hydrogenation active component, but the catalyst composition other than the hydrogenation active component needs to be separately examined and optimized for each type of hydrocarbon oil. This is common technical knowledge in this field. For example, when a so-called residual oil hydrogenation catalyst such as atmospheric distillation residual oil or vacuum distillation residual oil is used as a hydrogenation catalyst for distillate oil such as vacuum light oil, the catalyst of the hydrogenation catalyst for the residue. Since the molecules of the vacuum light oil are small with respect to the pore size, the diffusion rate-determining tends to occur, and the catalytic effect is difficult to obtain. Further, when a hydrogenation treatment catalyst for a relatively light oil type such as atmospheric distillation gas oil is used as a hydrogenation treatment catalyst for a relatively heavy oil type such as vacuum gas oil, the hydrogenation treatment catalyst for a relatively heavy oil type such as vacuum distilled gas oil is relatively high. Since an unfired catalyst is often used as a hydrogenation catalyst for light oil types, its activity tends to deteriorate in a high temperature environment such as hydrogenation treatment of reduced pressure gas oil.
The catalyst composition other than the hydrogenation active component is, for example, the specific surface area of the carrier, physical properties such as pore structure, the hydrogenation active component, the types of components (phosphorus, zinc, etc.) contained in the hydrogenation treatment catalyst other than alumina, and their components. The content ratio is given as an example.

The density of the heavy hydrocarbon oil used in the method for producing a hydrogenated heavy hydrocarbon oil of the present embodiment (method for hydrogenating a heavy hydrocarbon oil) is 0.91 to 1.10 g / cm ³ Is preferable, and 0.95 to 1.05 g / cm ³ is more preferable. The sulfur content is preferably 2 to 6% by mass, more preferably 2 to 5% by mass. The nickel content is preferably 3 ppm or less, the vanadium content is preferably 3 ppm or less, and the asphaltene content is preferably 0.1% by mass or less.

The density of the hydrogenated heavy hydrocarbon oil produced by the method for producing a hydrogenated heavy hydrocarbon oil of the present embodiment (the method for producing a hydrogenated heavy hydrocarbon oil) is 0.87 to 0.95 g /. cm ³ is preferable, and 0.88 to 0.94 g / cm ³ is more preferable. The sulfur content is preferably 1.0 to 3.5% by mass, more preferably 1.2 to 3.4% by mass.

The hydrogenation catalyst of the present embodiment may be activated by sulfurization treatment in a reactor before use (that is, prior to performing the hydrogenation treatment method of the present embodiment). This sulfurization treatment is generally carried out in a hydrogen atmosphere at 200 to 400 ° C., preferably 250 to 350 ° C., with a hydrogen partial pressure of normal pressure or higher, and petroleum distillates containing sulfur compounds, as well as dimethyl disulfide and disulfide. It can be carried out by adding a sulfurizing agent such as carbon or by passing hydrogen sulfide through a hydrogenation treatment catalyst.

Examples of zinc, phosphorus, Group 6 metal and cobalt contained in the catalyst of the present embodiment after the sulfurization treatment include zinc sulfide, phosphorus sulfide, sulfide of Group 6 metal and cobalt sulfide.
Further, a composite sulfide of two or more elements selected from the group consisting of zinc, phosphorus, Group 6 metal, cobalt and aluminum can be mentioned as an example.

By hydrogenating the heavy hydrocarbon oil using the hydrogenation treatment catalyst of the present embodiment, the hydrogenation treatment proceeds sufficiently and the sulfur compounds in the heavy hydrocarbon oil are reduced for a long period of time. It becomes possible.

In order to carry out the hydrogenation treatment method of the present embodiment on a commercial scale, a fixed bed, a moving bed, or a fluidized bed type catalyst layer of the hydrogenation treatment catalyst of the present embodiment is formed in the reaction device, and the inside of the reaction device is formed. The raw material oil may be introduced into the water, and the hydrogenation treatment may be carried out under the above conditions. Most commonly, a fixed bed catalyst layer is formed in the reactor, the feedstock oil is introduced into the upper part of the reactor, the fixed bed is passed from top to bottom, and the product flows out from the lower part of the reactor. On the contrary, the feedstock oil is introduced into the lower part of the reactor, the fixed bed is passed from the bottom to the top, and the product is discharged from the upper part of the reactor.

The hydrogenation treatment method of the present embodiment may be a one-stage hydrogenation treatment method in which the hydrogenation treatment catalyst of the present embodiment is filled in a single reaction device, or may be filled in some reaction devices. It may be a multi-stage continuous hydrogenation treatment method.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

<Physical and chemical properties of catalyst and carrier>
[1] Analysis of physical properties (specific surface area, pore volume, average pore diameter, and pore distribution)
a) Measurement method and equipment used:
-The specific surface area was measured by the BET method by nitrogen adsorption. As the nitrogen adsorption device, a surface area measuring device (Bellthorpe 28) manufactured by Nippon Bell Co., Ltd. was used.
-The pore volume, the average pore diameter, and the pore distribution were measured by the mercury intrusion method. As the mercury press-fitting device, a porosimeter (MICROMERITICS AUTO-PORE 9200: manufactured by Shimadzu Corporation) was used.

b) Measurement principle of mercury press-fitting method:
-The mercury press-fitting method is based on the law of capillarity. In the case of mercury and cylindrical pores, this law is expressed by: That is, the volume of mercury entering the pores as a function of the applied pressure P is measured. The surface tension of the pore mercury in the catalyst was 484 dyne / cm, and the contact angle was 130 °.
D =-(1 / P) 4γcosθ
In the formula, D is the pore diameter, P is the applied pressure, γ is the surface tension, and θ is the contact angle.
The pore volume is the total volume of mercury that has entered the pores per gram of catalyst or carrier. The average pore diameter is the average value of D calculated as a function of P.
The pore distribution is the distribution of D calculated with P as a function.

c) Measurement procedure:
1) Turn on the power of the vacuum heating deaerator and check that the temperature is 400 ° C and the degree of vacuum is 5 × 10 ^-2 Torr or less.
2) Leave the sample burette empty and hang it in a vacuum heating deaerator.
3) After confirming that the degree of vacuum is 5 × 10 ^-2 Torr or less, the sample burette is removed from the vacuum heating deaerator by closing its cock, cooled, and then weighed.
4) Place the sample (catalyst or carrier) in the sample burette.
5) Place the sample burette containing the sample in a vacuum heating deaerator and hold it for 1 hour or more after the ^{degree of vacuum becomes 5 × 10 -2 Torr or less.}
6) Remove the sample burette containing the sample from the vacuum heating deaerator, cool it, and measure the weight to determine the sample weight.
7) Place the sample in the cell for AUTO-PORE 9200.
8) Measured by AUTO-PORE 9200.

[2-1] Analysis of chemical composition a) Analytical method and equipment used:
-Metal analysis in the carrier and catalyst was performed using inductively coupled plasma emission spectrometry (ICPS-2000: manufactured by Shimadzu Corporation). _SO ^{4 2-analysis} in the catalyst, sulfur analyzer: was performed using (S632 LECO Corporation).
-Metal quantification was performed by the absolute calibration curve method.

b) Measurement procedure:
1) 0.05 g of the catalyst or carrier, 1 mL of hydrochloric acid (50% by mass), 1 drop of hydrofluoric acid, and 1 mL of pure water were added to Uniseal and heated to dissolve them.
2) After dissolution, the flask was transferred to a polypropylene volumetric flask (50 mL), pure water was added, and the mixture was weighed to 50 mL.
3) This solution was measured by ICPS-2000 or S632.

<Hydrogenation of heavy hydrocarbon oil>
Hydrogenation treatment of reduced pressure gas oil with the following properties was carried out in the following manner. First, the catalyst was filled in a high-pressure flow reactor to form a fixed-bed catalyst layer, which was pretreated under the following conditions. Next, a mixed fluid of the raw material oil heated to the reaction temperature and the hydrogen-containing gas is introduced from the upper part of the reactor, and the hydrogenation reaction of the desulfurization reaction and the decomposition reaction is allowed to proceed under the following conditions, and the product oil and the gas are produced. The mixed fluid of the above was drained from the lower part of the reactor, and the produced oil was separated by a gas-liquid separator.

Catalyst pretreatment conditions: Drying at 120 ° C. for 3 hours at normal pressure.
Pre-sulfurization of the catalyst was carried out with light oil under reduced pressure at a hydrogen partial pressure of 10.3 MPa and 370 ° C. for 12 hours. After that, it was switched to the raw material oil for activity evaluation.

Reaction conditions:
Pressure (hydrogen partial pressure); 4.9 MPa
Liquid space velocity; 0.95hr ^-1
Hydrogen / oil ratio; 240Nm ³ / kL
Reaction temperature: Set so that the sulfur content in the produced oil is 0.28% by mass.

Properties of raw material oil:
Oil type; reduced pressure light oil (Arabian heavy, Das blend)
Density (15 ° C); 0.9295 g / cm ³
Sulfur content; 2.72% by mass
Nitrogen content; 0.092% by mass
Residual carbon content; 0.81% by mass

[Manufacturing Example 1]
1.5 L of a 12 mass% sulfuric acid aqueous solution is put into 100 L of pure water filled in a stirring kettle, heated to 95 ° C., and then vigorously stirred with a stirring blade for 5 minutes, and there is sodium aluminate having an alumina concentration of 70 g / L. 3.9 L was charged to prepare aluminum hydroxide, and then the mixture was stirred with a stirring blade for 24 hours. The obtained slurry was put into a filter and filtered to remove water. Then, the resulting gel with pure water, SO 4 _2-in the filtrate ^was washed until Na ⁺ can not be detected. Next, the washed gel was turbid in pure water to form a uniform slurry, and the slurry was put into a squeeze type filter. The slurry was sandwiched between the filter plates via a filter cloth and dehydrated by pressing the filter plates. Filtration was interrupted when the water content in the cake reached 80% due to the dehydration. This cake was put into a heated kneader (set temperature 80 ° C.) and kneaded sufficiently so as to be uniform, and then phosphoric acid and zinc oxide were added and further kneaded so as to be uniform. The cake obtained by kneading was put into an extrusion molding machine to obtain a four-leaf shaped extruded product having a major axis of 1.3 mm and a minor axis of 1.1 mm. This molded product was dried and then calcined at 600 ° C. for 4 hours to obtain a phosphorus-zinc-containing alumina carrier (carrier A).
Table 1 shows the carrier standard of phosphorus and zinc of carrier A, the content in terms of oxide, the specific surface area, the pore volume, and the average pore diameter.

[Manufacturing Example 2]
An alumina carrier (carrier B) was obtained in the same manner as in Production Example 2 except that phosphoric acid and zinc oxide were not added.
Table 1 shows the carrier standard of phosphorus and zinc of carrier B, the content in terms of oxide, the specific surface area, the pore volume, and the average pore diameter.

[Example 1]
50.00 g of the carrier A produced in Production Example 1 was put into a eggplant-shaped flask, and 5.5114 g of cobalt carbonate, 19.0187 g of molybdric acid and 1.9418 g of orthoric acid were dissolved therein in 40.5 g of ion-exchanged water. The prepared solution was added with a pipette, soaked at 25 ° C. for 1 hour, air-dried in a nitrogen stream, dried in a muffle furnace at 120 ° C. for 1 hour, and then calcined at 500 ° C. for 4 hours to obtain catalyst A. Phosphorus catalyst A, zinc, cobalt, catalytic criteria molybdenum content as _{^{_{oxide, SO 4 2-, Na 2 O}}} , content of _Fe 2 _{O 3,} specific surface area, pore volume, average pore diameter, and Table 2 shows the ratio of the volume of pores having a pore diameter of ± 1.5 nm to the total pore volume. The "pore distribution" in Table 2 means "the ratio of the volume of pores having an average pore diameter of ± 1.5 nm to the total pore volume".
Using the catalyst A, the reaction temperature was adjusted so that the sulfur content in the produced oil was 0.28% by mass, and the heavy hydrocarbon oil was hydrogenated. Table 3 shows the reaction temperatures from 1 day to 17 days after the start of the reaction.

[Comparative Example 1]
A catalyst B was obtained in the same manner as in Example 1 except that the carrier B was used instead of the carrier A. The catalyst B has a catalyst standard for phosphorus, zinc, cobalt, and molybdenum, an oxide-equivalent content, a specific surface area, a pore volume, and an average pore diameter, and an average pore diameter of ± 1.5 nm with respect to the total pore volume. The volume ratio of the pores is shown in Table 2.
Using the catalyst B, the reaction temperature was adjusted so that the sulfur content in the produced oil was 0.28% by mass, and the heavy hydrocarbon oil was hydrogenated. Table 3 shows the reaction temperatures from 1 day to 12 days after the start of the reaction.

[Comparative Example 2]
60.00 g of the carrier A produced in Production Example 1 was put into a eggplant-shaped flask, and 11.1 g of nickel nitrate hexahydrate and 11.1 g of ammonium molybdate tetrahydrate were added to 36.1 g of ion-exchanged water. A solution prepared by dissolving 5 g and 13.8 g of citrate monohydrate acid was added with a pipette, soaked at 25 ° C. for 1 hour, air-dried in a nitrogen stream, dried in a muffle furnace at 120 ° C. for 1 hour, and 300. The mixture was calcined at ° C. for 1 hour and then at 500 ° C. for 4 hours to obtain a catalyst C. Phosphorus catalyst C, zinc, nickel, a catalyst based molybdenum, the content of the oxide in _{^{_{terms, SO 4 2-, Na 2 O}}} , content of _Fe 2 _{O 3,} specific surface area, pore volume, average pore diameter, and Table 2 shows the ratio of the volume of pores having a pore diameter of ± 1.5 nm to the total pore volume.
Using the catalyst C, the reaction temperature was adjusted so that the sulfur content in the produced oil was 0.28% by mass, and the heavy hydrocarbon oil was hydrogenated. Table 3 shows the reaction temperatures from 1 day to 17 days after the start of the reaction.

As shown in Table 3, the hydrogenation catalyst of the present invention of Example 1 has a lower reaction temperature at the initial stage of the reaction than the hydrogenation catalyst of Comparative Example 1 containing no zinc, and 17 days after the start of the reaction. However, it was not necessary to raise the reaction temperature. That is, it was found that the hydrogenation catalyst of Example 1 had higher hydrogenation treatment activity and was less likely to decrease in activity than the hydrogenation catalyst of Comparative Example 1.
Further, the hydrogenation catalyst of the present invention of Example 1 has a lower reaction temperature at the initial stage of the reaction than the hydrogenation catalyst of Comparative Example 2 containing no cobalt, and the reaction temperature is maintained even 17 days after the start of the reaction. I didn't have to raise it. It was considered that the reaction temperature at the initial stage of the reaction was largely due to the larger amount of molybdenum supported by the hydrogenation catalyst of Example 1 than that of the hydrogenation catalyst of Comparative Example 2. On the other hand, the increase in the reaction temperature was considered to be due to the fact that nickel was supported instead of cobalt in the hydrogenation catalyst of Comparative Example 2.

The hydrogenation treatment catalyst for heavy hydrocarbon oil according to the present invention is useful because it can be used to reduce the sulfur content in heavy hydrocarbon oil.

Claims

The carrier is phosphorus-zinc-containing alumina containing 0.1 to 4% by mass of phosphorus on a carrier basis and 0.1 to 8% by mass of zinc on a carrier basis, and 1 to 8% by mass on an oxide basis.
Heavy hydrocarbons on which at least one selected from Group 6 metals of the Periodic Table is supported on the carrier based on a catalyst, 8 to 30% by mass in terms of oxide, and cobalt is supported on a catalyst standard, 2 to 8% by mass in terms of oxide. Oil hydrogenation catalyst.
A phosphorus-zinc-containing alumina carrier containing 0.1 to 4% by mass of phosphorus on a carrier basis and 1 to 8% by mass on an oxide basis of zinc on a carrier basis from Group 6 metals of the periodic table. Hydrogen of heavy hydrocarbon oil having a step of supporting at least one selected so as to contain 8 to 30% by mass of oxide based on catalyst and 2 to 8% by mass of cobalt based on catalyst. A method for producing a chemical treatment catalyst.
Hydrogen / oil of the heavy hydrocarbon oil according to claim 1, having a hydrogen / oil ratio of 100 to 1000 Nm 3 / kL, a hydrogen partial pressure of 3.5 to 10 MPa, 330 to 430 ° C., and a liquid space velocity of 0.2 to 2 hr -1. A method for hydrogenating a heavy hydrocarbon oil, which comprises contact-treating a chemical treatment catalyst and a heavy hydrocarbon oil.