JP2015048397A - Method for producing hydrocarbon oil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing hydrocarbon oil capable of suppressing the inactivation of a desulfurization catalyst.SOLUTION: The method for producing hydrocarbon oil comprises: a demetallation step in which only solvent deasphalted oil is contacted with a demetallation catalyst in the presence of a hydrogen gas; and a desulfurization step in which the solvent deasphalted oil subjected to the demetallation step is contacted with a desulfurization catalyst in the presence of a hydrogen gas, the demetallation catalyst includes a low reactive catalyst, the ratio of the low reactive catalyst occupied in the demetallation catalyst is 50 vol.% or higher, the ratio of the high reactive catalyst occupied in the demetallation catalyst is 0 vol.% or higher, the low reactive catalyst contains a porous carrier and the group VI element(s) carried on the carrier, the content of the group VIII element(s) in the low reactive catalyst is 0 mass% or higher, the high reactive catalyst contains a porous carrier and the group VI element(s) and the group VIII element(s) carried on the carrier, and the content of the group VII element(s) in the low reactive catalyst is lower than the content of tthe group VIII element(s) in the high reactive catalyst.

Description

  The present invention relates to a method for producing a hydrocarbon oil.

  In the petroleum refining process, bottom tower oil (atmospheric residue, AR: atmospheric residue) is obtained by atmospheric distillation of crude oil. Products such as gasoline, base oils for lubricants, and other chemicals can be obtained by subjecting atmospheric residue and vacuum gas oil obtained by vacuum distillation of atmospheric residue to desulfurization and catalytic cracking. . On the other hand, the vacuum residue obtained by vacuum distillation of the atmospheric residue is a product with a lower profit margin than the above products. Therefore, it is desirable to produce products with higher profit margins from vacuum residue.

  The following Patent Document 1 prepares a raw material oil by mixing a solvent-removed oil (DAO: Desphailized Oil) obtained by solvent-removing a reduced-pressure residual oil with a normal-pressure residual oil and / or a reduced-pressure light oil. A technique for producing fuel such as gasoline by hydrorefining of oil is disclosed.

JP 2012-197350 A

  Generally, hydrorefining of feedstock includes a demetallization step and a subsequent desulfurization step. In the demetallation step, the metal oil (catalyst poison) that degrades the hydrodesulfurization catalyst is removed from the raw oil by bringing the raw oil into contact with the demetallation catalyst and hydrogenating it. In the desulfurization process, the sulfur in the raw material oil is removed by bringing the raw material oil after the demetallization process into contact with a desulfurization catalyst and hydrogenating it.

  As a result of the present inventors' research, the activity of a demetallization catalyst that removes metal components (demetallization) can be obtained by hydrorefining solvent debris by the same method as conventional hydrorefining of atmospheric residue. It has been found that the activity reached the lower limit earlier than expected, and the desulfurization activity of the desulfurization catalyst rapidly decreased following the deactivation of the demetallization catalyst. In other words, the hydrorefining of solvent debris oil using the conventional demetallation catalyst and desulfurization catalyst for atmospheric residual oil has a longer life of each catalyst compared to the hydrorefining of atmospheric residual oil. It will be shorter.

  This invention is made | formed in view of the subject which the said prior art has, and aims at providing the manufacturing method of the hydrocarbon oil which can suppress the deactivation of a desulfurization catalyst.

  One aspect of the method for producing a hydrocarbon oil according to the present invention includes a demetallation step in which only a solvent defragmentation oil is brought into contact with a demetallation catalyst in the presence of hydrogen gas, and a solvent defragmentation oil that has undergone the demetallation step. A desulfurization step of contacting the desulfurization catalyst in the presence of hydrogen gas, wherein the demetallation catalyst includes at least a low-reactivity catalyst, and the volume ratio of the low-reactivity catalyst to the entire demetallation catalyst is 50 volumes. % Of the volume of the highly reactive catalyst in the total demetallation catalyst is 0 volume% or more. The low reactivity catalyst is composed of a porous carrier, a Group VI element supported on the carrier, The content of the group VIII element based on the catalyst mass in the low-reactivity catalyst is 0% by mass or more, and the high-reactivity catalyst is composed of a porous carrier and a group VI supported on the carrier. Element and Group VIII element, and a low-reactivity catalyst Content of the catalyst based on the weight of the definitive group VIII element is lower than the content of the catalyst based on the weight of the Group VIII element in the highly reactive catalyst. Note that both the demetallation catalyst and the desulfurization catalyst have hydrogenation activity.

  The content of the group VI element based on the catalyst mass in the low-reactivity catalyst is preferably lower than the content of the group VI element based on the catalyst mass in the high-reactivity catalyst.

  Preferably, the Group VI element is at least one of molybdenum or tungsten, and the Group VIII element is at least one of nickel or cobalt.

  The content of the Group VI element oxide in the low-reactivity catalyst based on the catalyst mass is 1% by mass or more and less than 8% by mass, and the content of the Group VIII element oxide in the low-reactivity catalyst based on the catalyst mass The rate is preferably 0% by mass or more and less than 1% by mass.

In the demetallation step, the reaction temperature is 350 to 450 ° C., the hydrogen gas partial pressure is 5 to 25 MPa, the liquid space velocity (LHSV) is 0.1 to 3.0 h ⁻¹ , hydrogen The / oil ratio (ratio of the volume of hydrogen gas to the volume of solvent desorbed oil) is preferably 400 to 1500 Nm ³ / m ³ .

In the desulfurization step, the reaction temperature is 350 to 450 ° C., the partial pressure of hydrogen gas is 5 to 25 MPa, the liquid space velocity is 0.1 to 3.0 h ⁻¹ , and the hydrogen / oil ratio is 400 to 1500 Nm ³ / m ³ is preferable.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the hydrocarbon oil which can suppress the deactivation of a desulfurization catalyst is provided.

FIG. 1a is the molecular weight distribution of the vanadium compound in the solvent-desorbed oil, and FIG. 1b is the molecular weight distribution of the vanadium compound in the atmospheric residue.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiment.

  In one aspect of the method for producing hydrocarbon oil according to the present invention, bottom tower oil (atmospheric residual oil) is obtained by atmospheric distillation of crude oil. The atmospheric residue is a heavy oil having a fraction having a boiling point of 343 ° C. or higher and a content of 80% by mass or higher. A vacuum gas oil and a vacuum residue are obtained by vacuum distillation of the atmospheric residue. Although the kind of crude oil is not particularly limited, specific examples of crude oil include petroleum-based crude oil, synthetic crude oil derived from oil sand, and bitumen reformed oil.

  Hydrocarbon oil is obtained by desulfurization (for example, hydrodesulfurization) of vacuum gas oil and fluid catalytic cracking or hydrocracking after desulfurization. Similarly, hydrocarbon oil is obtained by desulfurization of atmospheric residue and catalytic cracking or hydrocracking after desulfurization.

  Solvent degreased oil is obtained by solvent debris removal of the vacuum residue. The solvent deasphalting oil is a fraction obtained by extracting a heavy oil (for example, a vacuum residue) having a boiling point of 550 ° C. or higher and a fraction having a boiling point of 550 ° C. or higher with a solvent. As the solvent used for solvent removal, a chain saturated hydrocarbon having 3 to 6 carbon atoms may be used. Specific examples of the solvent include propane, normal butane, isobutane, normal pentane, isopentane, and normal hexane. One or more of these solvents may be used as the solvent.

  The manufacturing method of the hydrocarbon oil which concerns on this embodiment is equipped with the demetallation process using the said solvent debris oil, and the desulfurization process following this. In the demetallation step, only solvent degreasing oil is brought into contact with the demetallation catalyst in the presence of hydrogen gas. As a result, the metal component in the solvent removal solvent is removed. In the desulfurization step, the solvent debris oil after the demetallation step is brought into contact with the desulfurization catalyst in the presence of hydrogen gas. As a result, the sulfur content (and nitrogen content) in the solvent removal solvent is removed. Hydrocarbon oil is obtained by fluid catalytic cracking or hydrocracking of solvent debris oil that has undergone the demetallization process and the desulfurization process.

  In the demetallation step, by removing the metal component which is a catalyst poison for the desulfurization catalyst from the solvent deasphalted oil, it is possible to suppress the deactivation of the desulfurization catalyst in the desulfurization step and extend the life of the desulfurization catalyst.

  Below, a demetallation process and a desulfurization process are demonstrated in detail.

  The metal-containing compound is a substance containing a metal and a hydrocarbon. The structure of the metal-containing compound is not particularly limited. For example, the hydrocarbon and the metal may form a chemical bond (for example, coordination bond), or the hydrocarbon may cover the fine metal. The metal is, for example, vanadium or nickel. The hydrocarbon is not particularly limited, and may be, for example, a chain hydrocarbon or an isomer thereof, a cyclic hydrocarbon, a heterocyclic compound, or an aromatic hydrocarbon. The smaller the molecular weight of the metal-containing compound, the easier the hydrogenation and decomposition of the metal-containing compound by the demetallation catalyst, and the easier the metal is removed from the metal-containing compound. The metal removed from the metal-containing compound is taken into countless pores formed in the demetallation catalyst and removed in the demetallation step.

  As described above, the smaller the molecular weight of the metal-containing compound, the easier the metal is taken into the demetallation catalyst. Hereinafter, a metal-containing compound having a relatively low molecular weight is referred to as “decomposable metal component”. In addition, a metal-containing compound having a relatively large molecular weight is referred to as “persistent metal composition”. A metal-containing compound having vanadium is referred to as a vanadium-containing compound.

  FIG. 1a shows the molecular weight distribution (hereinafter referred to as “DAO distribution”) of the vanadium-containing compound in the solvent-desorbed oil. This DAO distribution is obtained by the following experiment conducted by the present inventors.

  In the experiment, solvent permeation oil is fractionated by the difference in molecular weight using gel permeation chromatography (GPC: Gel Permeation Chromatography). The molecular weight of each fractionated component is a polystyrene equivalent molecular weight (relative molecular weight) determined from a calibration curve using polystyrene as a standard sample. The mass conversion or molar conversion concentration of metal (vanadium) in each component fractionated by GPC is measured by inductively coupled plasma (ICP) emission spectroscopic analysis. The horizontal axis of FIG. 1a is a value based on the GPC, and is the molecular weight of the vanadium-containing compound. The scale on the horizontal axis is a logarithmic scale. The vertical axis of FIG. 1a is a value corresponding to the vanadium concentration measured by the ICP emission spectroscopic analysis, and is the amount of vanadium at each molecular weight shown on the horizontal axis.

  FIG. 1 b shows the molecular weight distribution of the vanadium-containing compound in the atmospheric residue (hereinafter referred to as “AR distribution”). This AR distribution was obtained by the present inventors based on GPC and ICP emission spectroscopic analysis of atmospheric residual oil as in the case of the DAO distribution.

  The DAO distribution in FIG. 1a has one peak at a low molecular weight. The DAO distribution indicates that the metal component (vanadium component) is small in the region where the molecular weight is large. On the other hand, the AR distribution in FIG. 1b shows that a large amount of metal component (vanadium component) is present from a region having a low molecular weight to a region having a high molecular weight, in contrast to the DAO distribution. In other words, most of the metal component (vanadium component) contained in the solvent-peeling oil is an easily decomposable metal component. In contrast, atmospheric residual oil is not only an easily decomposable metal component but also a large amount of hardly decomposable metal. Contains ingredients.

  If the demetalization process is performed using atmospheric residual oil instead of solvent degreasing oil, the atmospheric residual oil contains not only readily decomposable metal components but also a large amount of hardly decomposable metal components. The higher the hydrogenation activity of the catalyst, the easier the metal component is removed from the atmospheric residue.

  On the other hand, most of the metal components contained in the solvent-peeling oil are easily decomposable metal components. Therefore, when the hydrogenation activity of the demetallation catalyst used in the demetallation step of solvent debris oil is as high as that of the demetallation catalyst for atmospheric residual oil, the hydrogenation of easily decomposable metal components is The process proceeds excessively in a short period of time. As a result, an excessive amount of metal derived from the metal component accumulates in the vicinity of the surface of the demetallization catalyst within a short period of time, blocking the pore inlet formed in the demetallization catalyst, and the metal becomes the pores of the catalyst. It becomes difficult to be taken in. That is, when the hydrogenation activity of the demetallation catalyst for solvent debris oil is too high, it becomes difficult to remove the metal component from the solvent debris oil. As a result, in the desulfurization process after the demetallization process, the metal component remaining in the solvent degassed oil deactivates the desulfurization catalyst.

  The inventors have clarified by experiments that when atmospheric residue is brought into contact with a demetallation catalyst having high hydrogenation activity, metal is deposited not only near the surface of the demetallation catalyst but also inside the demetalization catalyst. did. In addition, when the present inventors contact the solvent degreasing oil with a demetallation catalyst having a high hydrogenation activity, the amount of metal deposited near the surface of the demetallation catalyst is significantly higher than the amount of metal deposited inside the demetallation catalyst. It was clarified by experiment that it would increase. These experimental results support the deactivation mechanism of the demetallation catalyst.

  Then, the present inventors have found the following demetalization catalyst which is difficult to deactivate based on the above knowledge about the relationship between the molecular weight of the vanadium-containing compound and the demetallation activity of the demetallation catalyst.

  In this embodiment, the demetallation catalyst includes at least a low-reactivity catalyst. This low-reactivity catalyst is a catalyst having a low hydrogenation activity as compared with a high-reactivity catalyst suitable for a conventional demetallation step of atmospheric residue. The ratio of the volume of the low-reactivity catalyst to the entire demetallation catalyst is 50% by volume or more and 100% by volume or less. The proportion of the volume of the low-reactivity catalyst in the total demetallation catalyst may be 60% by volume or more, 70% by volume or more, 80% by volume or more, or 90% by volume or more. On the other hand, the ratio of the volume of the highly reactive catalyst to the whole demetalization catalyst is 0% by volume or more and less than 50% by volume. The proportion of the volume of the highly reactive catalyst in the entire demetallation catalyst may be 40% by volume or less, 30% by volume or less, 20% by volume or less, and 10% by volume or less. The demetallation catalyst may consist only of a low-reactivity catalyst. That is, the demetallation catalyst does not need to contain a highly reactive catalyst.

  In this embodiment, since the volume ratio of the low-reactivity catalyst in the demetalization catalyst is within the above range, hydrogenation of the easily decomposable metal component in the solvent debris oil proceeds rapidly on the demetallation catalyst surface. The phenomenon is suppressed. As a result, a phenomenon in which an excessive amount of metal derived from the metal component accumulates in the vicinity of the surface of the demetallization catalyst in a short period of time is suppressed, and the entrance of the pores formed in the demetallization catalyst is difficult to be blocked by the metal. . Therefore, in the present embodiment, the metal is easily taken into the pores of the catalyst for a long period of time, and the metal component is easily removed from the solvent desorbing oil. As a result, it is difficult for the metal component to remain in the solvent deasphalted oil after the demetallation step, and the phenomenon that the metal component deactivates the desulfurization catalyst in the desulfurization step is suppressed. That is, the lifetime of the desulfurization catalyst is extended.

  When the demetallation catalyst includes both a low-reactivity catalyst and a high-reactivity catalyst, the demetallation catalyst consists of a low-reactivity catalyst part (low-reactivity catalyst layer) composed of a low-reactivity catalyst, and a high-reactivity catalyst. It is preferable to comprise a highly reactive catalyst portion (highly reactive catalyst layer). And it is preferable to make solvent deasphalted oil contact a highly reactive catalyst part after making it contact a low reactive catalyst part. In this case, the phenomenon in which hydrogenation of the easily decomposable metal component proceeds rapidly on the surface of the highly reactive catalyst is suppressed, and the entrance of the pores formed in the highly reactive catalyst is less likely to be blocked by the metal.

  The low-reactivity catalyst has a porous support and a Group VI element supported on the support. The content of the Group VIII element in the low-reactivity catalyst based on the catalyst mass is 0% by mass or more. On the other hand, the highly reactive catalyst has a porous carrier and a Group VI element and a Group VIII element supported on the carrier. The content of the group VIII element based on the catalyst mass in the low-reactivity catalyst is lower than the content of the group VIII element based on the catalyst mass in the high-reactivity catalyst.

  Since the low-reactivity catalyst and the high-reactivity catalyst have the above composition, the hydrogenation activity of the low-reactivity catalyst is lower than the hydrogenation activity of the high-reactivity catalyst. It becomes possible to suppress the deactivation.

The porous carrier that the low-reactivity catalyst or the high-reactivity catalyst has is not particularly limited. Specific examples of the porous carrier include inorganic oxides such as alumina, silica, and silica-alumina. The carrier of the low reactivity catalyst and the carrier of the high reactivity catalyst may be the same or different. The center pore diameter of each demetallation catalyst is preferably 10 to 50 nm. The median pore diameter is the cumulative volume of pores having each diameter when V is the cumulative pore volume of pores having a pore diameter of 2 nm or more and less than 60 nm obtained by the nitrogen gas adsorption method. In the cumulative pore volume curve, it means the pore diameter at which the cumulative pore volume is V / 2. When the central pore diameter is within the above range, the metal derived from the metal component is easily taken into the demetallation catalyst, and deactivation of the desulfurization catalyst is easily suppressed. The pore volume of each demetallizing catalyst may be about 0.5 to 1.5 cm ³ / g. The BET specific surface area of each demetallization catalyst should just be about 100-250 m < ² > / g.

  The Group VI element belongs to the short periodic table (old periodic table) and corresponds to the Group 6 element of the long periodic table (new periodic table) in the IUPAC format. That is, the Group VI element is at least one selected from the group consisting of chromium, molybdenum, tungsten, and seaborgium. The Group VIII element belongs to the short periodic table and corresponds to the Group 8 element, the Group 9 element, and the Group 10 element of the long periodic table in the IUPAC format. That is, the group VIII element is at least one selected from the group consisting of iron, ruthenium, osmium, hashium, cobalt, rhodium, iridium, miterium, nickel, palladium, platinum, and dermstatium. The Group VI element included in the low-reactivity catalyst and the Group VI element included in the high-reactivity catalyst may be the same or different. The Group VIII element included in the low-reactivity catalyst and the Group VIII element included in the high-reactivity catalyst may be the same or different.

  In the said aspect, it is preferable that the content rate of the catalyst mass reference | standard of the group VI element in a low-reactivity catalyst is lower than the content rate of the catalyst mass reference | standard of the group VI element in a highly reactive catalyst. In this case, the hydrogenation activity of the low-reactivity catalyst tends to be lower than the hydrogenation activity of the high-reactivity catalyst.

  The Group VI element included in the low-reactivity catalyst or the high-reactivity catalyst is preferably at least one of molybdenum and tungsten, and more preferably molybdenum. When the low-reactivity catalyst or the high-reactivity catalyst has these Group VI elements, deactivation of the demetallation catalyst and desulfurization catalyst is remarkably suppressed. The Group VIII element contained in the low-reactivity catalyst or the high-reactivity catalyst is preferably at least one of nickel and cobalt, and more preferably nickel. When the highly reactive catalyst has these Group VIII elements, deactivation of the demetallation catalyst and the desulfurization catalyst is remarkably suppressed.

In the said aspect, it is preferable that the catalyst mass reference | standard content rate of the oxide of the group VI element in a low-reactivity catalyst is 1 to 8 mass%, and it is 1 to 6 mass%. Is more preferable. The content of the catalyst based on the mass of the Group VIII element oxide in the low-reactivity catalyst is preferably 0% by mass or more and less than 1% by mass. When the lower limit of the content of the Group VI element oxide or Group VIII element oxide in the low-reactivity catalyst is the above value, the low-reactivity catalyst can have sufficient hydrogenation activity. In addition, when the upper limit of the content of the Group VI element oxide or the Group VIII element oxide in the low-reactivity catalyst is the above value, rapid hydrogenation of the easily decomposable metal component is suppressed, The demetalization activity of the demetallation catalyst is easily maintained. The Group VI element oxide is, for example, MoO ₃ or WO ₃ . The oxide of the Group VIII element is, for example, NiO or CoO.

  The content of the Group VI element oxide in the highly reactive catalyst based on the catalyst mass may be 8% by mass or more and 30% by mass or less. The content of the catalyst based on the mass of the Group VIII element oxide in the highly reactive catalyst may be 1% by mass or more and 10% by mass or less. When the content of the Group VI element oxide or the Group VIII element oxide in the highly reactive catalyst is in the above range, the effect of the present invention is easily obtained.

The desulfurization catalyst is not particularly limited. As the desulfurization catalyst, a catalyst having a porous carrier and an active metal supported on the carrier may be used. As the carrier, alumina, silica, or silica-alumina may be used. As the active metal, at least one of the Group 5 element, Group 6 element, Group 8 element, Group 9 element, and Group 10 element of the long periodic table may be used. In particular, the active metal is preferably a combination of at least one of nickel and cobalt and at least one of molybdenum and tungsten. Specific examples include Ni—Mo, Co—Mo, and Ni—Co—Mo. The central pore diameter of the desulfurization catalyst may be about 8 to 12 nm. The pore volume of the desulfurization catalyst may be about 0.4 to 1.0 cm ³ / g. The BET specific surface area of a desulfurization catalyst should just be about 180-250 m < ² > / g.

  The shapes of the demetallation catalyst and the desulfurization catalyst are not particularly limited. The shape of each catalyst may be, for example, a prismatic shape, a cylindrical shape, a three-leaf shape, a four-leaf shape, or a spherical shape. The size of each catalyst is not particularly limited, but the particle size of the demetallation catalyst may be about 1 to 8 mm, and the particle size of the desulfurization catalyst may be about 0.8 to 3.0 mm.

It is preferable to carry out the hydrogenation treatment (demetallation) of the solvent debris oil in the demetallation step under the following reaction conditions.
Reaction temperature (temperature of demetallation catalyst): 350-450 ° C. More preferably, it is 350-410 degreeC.
Partial pressure of hydrogen gas in the reaction field: 5 to 25 MPa. More preferably, it is 10-20 MPa.
Liquid space velocity (LHSV): 0.1-3.0 h < ^-1 >. More preferably 0.1 to 2.0 h ⁻¹ .
Hydrogen / oil ratio: 400~1500Nm ³ / ^{m 3.} More preferably 500~1200Nm ³ / ^{m 3.}

The hydrodesulfurization of solvent debris oil in the desulfurization step is preferably performed under the following reaction conditions.
Reaction temperature (temperature of the desulfurization catalyst): 350 to 450 ° C. More preferably, it is 350-430 degreeC.
Partial pressure of hydrogen gas in the reaction field: 5 to 25 MPa. More preferably, it is 10-20 MPa.
Liquid space velocity (LHSV): 0.1-3.0 h < ^-1 >. More preferably 0.1 to 2.0 h ⁻¹ .
Hydrogen / oil ratio: 400~1500Nm ³ / ^{m 3.} More preferably 500~1200Nm ³ / ^{m 3.}

  By carrying out the demetallation step and the desulfurization step under the above conditions, deactivation of the demetallation catalyst and the desulfurization catalyst is easily suppressed, and the concentration of sulfur in the solvent debris oil after the desulfurization step is 0.6 mass. It becomes possible to reduce to less than%.

  When the reaction temperature in a demetallation process or a desulfurization process is more than the said lower limit, it will become easy to reduce the content rate of the sulfur content in the solvent debris oil after a desulfurization process. When the reaction temperature is equal to or lower than the above upper limit value, the coking reaction is easily suppressed, and a differential pressure in the reactor (reaction tower) in which the demetallation step or the desulfurization step is performed is difficult to occur.

  When the partial pressure of hydrogen gas in the demetallation step or the desulfurization step is equal to or higher than the lower limit value, the demetallation and desulfurization reaction easily proceeds, and the deactivation of the demetallation catalyst and the desulfurization catalyst is easily suppressed. When the partial pressure of the hydrogen gas is equal to or higher than the above upper limit value, high pressure resistance is required for the reaction tower or the consumption amount of the hydrogen gas increases, so that the economic efficiency of the demetallization process or the desulfurization process is not good.

When the liquid space velocity of the solvent debris oil in the demetalization step or desulfurization step is less than the lower limit value, the amount of solvent debris oil treated is small, and the economics of the demetallation step or desulfurization step are not good.
When the liquid space velocity is not more than the above upper limit value, the demetallation catalyst and the desulfurization catalyst are hardly deactivated, and the reaction temperature is easily maintained at a low level.

  When the hydrogen / oil ratio is equal to or higher than the lower limit, deactivation of the demetallation catalyst and the desulfurization catalyst is easily suppressed. When the hydrogen / oil ratio is equal to or higher than the above upper limit value, the tendency for the deactivation of each catalyst to be suppressed by the increase in the hydrogen / oil ratio becomes moderate.

  The reaction conditions for the demetallization process may differ from the reaction conditions for the desulfurization process. After performing the demetallization process in one reaction tower, the desulfurization process may be performed in another reaction tower. The demetallation catalyst and the desulfurization catalyst may be installed in the same reaction tower, and the demetallation step and the desulfurization step may be continuously performed under the same reaction conditions. In this case, a demetallization catalyst part (demetallization catalyst layer) composed of a demetallization catalyst and a desulfurization catalyst part (desulfurization catalyst layer) composed of a desulfurization catalyst are provided, and solvent debris oil is removed from the demetallization catalyst part. After contacting, the desulfurization catalyst part may be contacted.

  The ratio of the vanadium content in the vanadium-containing compound having a molecular weight (polystyrene equivalent molecular weight) of 3000 or less in the vanadium content in all vanadium-containing compounds in the solvent-desorbed oil is the vanadium content in all vanadium-containing compounds. It is preferable that it is 80 mass% or more with respect to it. In this case, deactivation of the demetallation catalyst and desulfurization catalyst is remarkably suppressed.

  Hereinafter, although the content of the present invention is explained in detail using an example and a comparative example, the present invention is not limited to the following examples.

(Example 1)
The demetallation process and desulfurization process using only solvent deasphalted oil were carried out by the following procedure.

The properties of the solvent removal oil used were as follows.
Sulfur content: 4.7% by mass.
Vanadium content: 42 mass ppm.
Nickel content: 21 ppm by mass.
Asphaltene content: 0.2% by mass.
Density at 15 ° C .: 1.01 g / cm ³ .
Kinematic viscosity at 100 ° C .: 456 mm ² / s.
Residual carbon content: 14.4% by mass.
Nitrogen content: 0.24% by mass.

A method for analyzing the above-described properties of the solvent-peeling oil is as follows.
Sulfur content: JIS K2541 “Crude oil and petroleum products—sulfur content test method”.
Vanadium and nickel content: JIS K0116 “General Rules for Emission Spectroscopy”.
Content of asphaltenes: IP-143 (ASTM D6560) “Determination of Asphaltenes in Crude Petroleum and Petroleum Products”.
Density at 15 ° C .: JIS K2249 “Crude oil and petroleum products—density test method and density / mass / volume conversion method”.
Kinematic viscosity at 100 ° C .: JIS K2283 “Crude oil and petroleum products—Kinematic viscosity test method and viscosity index calculation method”.
Residual carbon content: JIS K2270 “Crude oil and petroleum products—residual carbon content test method”.
Nitrogen content: JIS K2609 "Crude oil and petroleum products-nitrogen content test method".

  The molecular weight distribution of the vanadium-containing compound in the solvent-peeling oil was measured by the above GPC and ICP emission spectroscopic analysis. The vanadium content in the vanadium-containing compound having a molecular weight of 3000 or less was 94% by mass with respect to the vanadium content in all the vanadium-containing compounds in the solvent-desorbed oil. GPC and ICP emission spectroscopic analysis were performed under the following conditions.

[GPC conditions]
Mobile phase: Mixed solvent of tetrahydrofuran (THF) and o-xylene.
Volume ratio of THF to o-xylene in mobile phase: 30%: 70%.
Flow rate of moving bed: 0.8 mL / min.
Measurement time: 20 minutes.
Column type: Shodex ^™ KF-G and KF-803.
Column oven temperature: 40 ° C
RI attendant: x4.
RI polarity: +.
* Device name: HP1100 manufactured by Agilent.

[Conditions for ICP emission spectroscopic analysis]
Observation height: 20.0 mm.
RF output: 1.5 kW.
Photomultiplier tube voltage: High.
Measurement wavelength: 309.311 nm.
Spectroscope: R.
A / D attendant: 1/4.
* Device name: SPS3100 manufactured by SII Nanotechnology.

  The demetalization catalyst and the desulfurization catalyst were packed in the reaction tower as follows.

  The first catalyst layer, the second catalyst layer, and the third catalyst layer were laminated in this order in the reaction tower. A 1st catalyst layer is a layer which consists only of the low-reactive catalyst which is a demetallation catalyst. A 2nd catalyst layer is a layer which consists only of the highly reactive catalyst which is a demetallation catalyst. A 3rd catalyst layer is a layer which consists only of a desulfurization catalyst. The ratio of the volume of the first catalyst layer (low-reactivity catalyst) to the total volume of the first catalyst layer and the second catalyst layer (total volume of the demetallation catalyst) was 50% by volume. The ratio of the volume of the second catalyst layer (highly reactive catalyst) to the total volume of the first catalyst layer and the second catalyst layer (total volume of the demetalized catalyst) was 50% by volume. The volume of the third catalyst layer was the same as the sum of the volumes of the first catalyst layer and the second catalyst layer.

The low-reactivity catalyst was provided with porous γ-alumina, and MoO ₃ and NiO supported on γ-alumina. The supported amount (content rate) of MoO _{3 in} the low-reactivity catalyst was 5.0% by mass with respect to the total mass of the low-reactivity catalyst. The supported amount (content rate) of NiO in the low-reactivity catalyst was 0.5% by mass with respect to the total mass of the low-reactivity catalyst. The median pore diameter of the low-reactivity catalyst (γ alumina) was 18 nm. The BET specific surface area of the low-reactivity catalyst was 180 m ² / g.

The highly reactive catalyst comprises porous γ alumina and MoO ₃ and NiO supported on γ alumina. The supported amount (content rate) of MoO _{3 in} the highly reactive catalyst was 9.0% by mass with respect to the total mass of the highly reactive catalyst. The supported amount (content ratio) of NiO in the highly reactive catalyst was 2.0% by mass with respect to the total mass of the highly reactive catalyst. The central pore diameter of the highly reactive catalyst (γ alumina) was 19 nm. The BET specific surface area of the highly reactive catalyst was 180 m ² / g.

The desulfurization catalyst was provided with porous γ alumina and MoO ₃ and NiO supported on γ alumina. The supported amount (content) of MoO _{3 in} the desulfurization catalyst was 12.0% by mass with respect to the total mass of the desulfurization catalyst. The supported amount (content rate) of NiO in the desulfurization catalyst was 3.0% by mass with respect to the total mass of the desulfurization catalyst. The median pore diameter of the desulfurization catalyst (γ alumina) was 10 nm. The BET specific surface area of the desulfurization catalyst was 230 m ² / g.

  In the demetallization process and the desulfurization process, the solvent debris oil is introduced into the first catalyst layer in the reaction tower where hydrogen gas is present, and the solvent debris oil that has passed through the first catalyst layer is introduced into the second catalyst layer. The solvent-peeling oil that passed through the second catalyst layer was introduced into the third catalyst layer. Thus, the demetallation process and the desulfurization process were continuously implemented. The reaction conditions of the demetallation step and the desulfurization step were as follows.

[Reaction conditions]
Initial reaction temperature (temperature of each catalyst layer)
First catalyst layer and second catalyst layer (demetallized catalyst): 360 ° C.
Third catalyst layer (desulfurization catalyst): 370 ° C.
Partial pressure of hydrogen gas in the reaction tower: 14.4 MPa.
Liquid space velocity: 0.44 h < ^-1 >.
Hydrogen / oil ratio: 900 Nm ³ / m ³ .

  In the demetallization process and the desulfurization process, the activities of the demetallization catalyst and the desulfurization catalyst decrease with the passage of time. Therefore, in the demetallization process and the desulfurization process, the reaction temperature was increased by heating the inside of the reaction tower with a heater provided in the reaction tower as time passed, thereby supplementing the activities of the demetallation catalyst and the desulfurization catalyst. By supplementing the activity of each catalyst, the sulfur content in the solvent desorbed oil that passed through the third catalyst layer (the solvent desorbed oil after the demetallation step and the desulfurization step) was maintained at less than 0.6% by mass. . Then, the number of days until the reaction temperature reached the heat resistant temperature of 400 ° C. of the reaction tower from the start time of the demetallation step and the desulfurization step was measured. This number of days is called the absolute life of the desulfurization catalyst. The value obtained by dividing the absolute life by 300 days is referred to as the relative life of the desulfurization catalyst. The absolute life and relative life of the desulfurization catalyst in Example 1 are shown in Table 1 below.

(Examples 2 and 3 and Comparative Examples 1 to 4)
In Examples 2 and 3 and Comparative Examples 1 to 4, the volume of the first catalyst layer (low-reactive catalyst) in the total volume of the first catalyst layer and the second catalyst layer (total volume of the demetallized catalyst) The ratio was adjusted to the value shown in Table 1. In Examples 2 and 3 and Comparative Examples 1 to 4, the second catalyst layer (highly reactive catalyst) occupies the total volume of the first catalyst layer and the second catalyst layer (total volume of the demetallized catalyst). The volume ratio was adjusted to the values shown in Table 1. Except for the volume ratio of each catalyst layer, the demetallation step and the desulfurization step of Examples 2 and 3 and Comparative Examples 1 to 4 were performed in the same manner as in Example 1. In Comparative Example 1, only the second catalyst layer (high reactivity catalyst) was used as the demetallation catalyst without using the first catalyst layer (low reactivity catalyst). On the other hand, in Example 3, only the first catalyst layer (low-reactivity catalyst) was used as the demetallation catalyst without using the second catalyst layer (high-reactivity catalyst).

  The absolute life and relative life of the desulfurization catalysts in Examples 2 and 3 and Comparative Examples 1 to 4 measured by the same method as in Example 1 are shown in Table 1 below.

  As shown in Table 1, in Examples 1 to 3 in which the ratio of the volume of the low-reactive catalyst to the entire metal catalyst is 50% by volume or more, the life of the desulfurization catalyst is longer than that in Comparative Examples 1 to 4. Was confirmed. That is, in Examples 1 to 3, it was confirmed that deactivation of the desulfurization catalyst was suppressed. In view of the fact that the deactivation of the desulfurization catalyst is caused by the deactivation of the demetallization catalyst, it was confirmed in Examples 1 to 3 that the deactivation of the demetallization catalyst was suppressed compared to Comparative Examples 1 to 4. It was done.

  The method for producing a hydrocarbon oil according to the present invention is suitable for producing gasoline, base oil for lubricating oil, other chemicals, etc. using solvent-desorbed oil as a raw material.

Claims (6)

A demetallation step in which only solvent degreasing oil is brought into contact with a demetallation catalyst in the presence of hydrogen gas;
A desulfurization step in which the solvent deasphalted oil that has undergone the demetallization step is brought into contact with a desulfurization catalyst in the presence of hydrogen gas;
With
The demetallation catalyst includes at least a low-reactivity catalyst,
The volume ratio of the low-reactivity catalyst to the whole demetalization catalyst is 50% by volume or more,
The volume ratio of the highly reactive catalyst in the total demetallation catalyst is 0% by volume or more,
The low-reactivity catalyst has a porous carrier and a Group VI element supported on the carrier,
The content of catalyst group based on the group VIII element in the low-reactivity catalyst is 0% by mass or more,
The highly reactive catalyst has a porous carrier, and a Group VI element and a Group VIII element supported on the carrier,
The content of the group VIII element catalyst mass basis in the low-reactivity catalyst is lower than the content of the group VIII element catalyst mass basis in the high-reactivity catalyst;
A method for producing hydrocarbon oil. The content of the group VI element based on catalyst mass in the low-reactivity catalyst is lower than the content of the group VI element based on catalyst mass in the high-reactivity catalyst,
The method for producing a hydrocarbon oil according to claim 1. The Group VI element is at least one of molybdenum and tungsten;
The Group VIII element is at least one of nickel and cobalt;
The manufacturing method of the hydrocarbon oil of Claim 1 or 2. The content of the catalyst based on the mass of the Group VI element oxide in the low-reactivity catalyst is 1% by mass or more and less than 8% by mass,
The catalyst mass-based content of the Group VIII element oxide in the low-reactivity catalyst is 0% by mass or more and less than 1% by mass,
The manufacturing method of the hydrocarbon oil as described in any one of Claims 1-3. In the demetalization step,
The reaction temperature is 350-450 ° C.,
The partial pressure of the hydrogen gas is 5 to 25 MPa,
The liquid space velocity is 0.1 to 3.0 h ⁻¹ ;
The hydrogen / oil ratio is 400-1500 Nm ³ / m ³ ,
The manufacturing method of the hydrocarbon oil as described in any one of Claims 1-4. In the desulfurization step,
The reaction temperature is 350-450 ° C.,
The partial pressure of the hydrogen gas is 5 to 25 MPa,
The liquid space velocity is 0.1 to 3.0 h ⁻¹ ;
The hydrogen / oil ratio is 400-1500 Nm ³ / m ³ ,
The manufacturing method of the hydrocarbon oil as described in any one of Claims 1-5.

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