JPWO2016194686A1 - Method for producing hydrotreated oil and method for producing catalytic cracking oil - Google Patents

Abstract

A heavy hydrocarbon oil is passed through a reactor filled with a hydroprocessing catalyst to obtain a hydroprocessing oil, and the hydroprocessing catalyst contains phosphorus, an iron group element, and a group 6 element. The ratio C2 / C1 of the iron group element content C2 to the phosphorus content C1 in the hydroprocessing catalyst is less than 0.60 in terms of molar ratio, and the average pore diameter of the hydroprocessing catalyst is 7.5 nm. A process for producing hydrotreated oil that is larger and smaller than 9.5 nm.

Description

  The present invention relates to a production method for obtaining hydrotreated oil from heavy hydrocarbon oil, and a production method for obtaining catalytic cracked oil from heavy hydrocarbon oil.

  Until now, in the refineries in Japan, fluid catalytic cracking (FCC) equipment has played a central role in gasoline production in order to meet the demand for gasoline and promote the lightening of heavy hydrocarbon oils. In recent years, there has also been a great interest in FCC equipment as a process for producing light hydrocarbon oils with high added value from heavy hydrocarbon oils, and demanded higher economic efficiency. In addition to the above components, raw material oils mixed with residual oils such as atmospheric residue fractions are also used.

  Since atmospheric pressure residual oil contains heavy metals such as vanadium and nickel in addition to sulfur and nitrogen, a catalyst is installed in the heavy oil direct desulfurization unit that is the pretreatment of the FCC unit, and the reaction is performed under high temperature and high pressure conditions. Demetallization, desulfurization and denitrification.

  By the way, zeolite is generally used for the FCC catalyst used in the FCC apparatus. In the FCC feedstock, reduction of nitrogen content, especially basic nitrogen content, that poisons zeolite has been desired. That is, it is considered that if the nitrogen content in the FCC feedstock can be reduced, the performance of the FCC catalyst will be sufficiently exerted and the efficiency of gasoline production will be improved. However, until now, it is believed that if the desulfurization reaction proceeds in the heavy hydrocarbon oil direct desulfurization apparatus, the denitrogenation reaction also proceeds, and there has been no technique for improving the denitrification activity.

  Although it is hoped that the nitrogen content in heavy hydrocarbon oils will be reduced, it has so far been primarily aimed at reducing the sulfur content, and also protects the desulfurization catalyst that removes the sulfur content. Attention has been focused on the development of demetallization catalysts, which is a role to play.

  For example, in Non-Patent Document 1, by impregnating and supporting phosphorus, desulfurization activity and denitrogenation activity are improved, while catalyst pore volume decreases, causing rapid metal poisoning and shortening catalyst life. It is described that there is a tendency.

  Until now, many reports have been made on the hydrotreating method of FCC feedstock. For example, in Patent Documents 1 and 2, the first step of performing desulfurization and denitrogenation treatment at a relatively high reaction temperature, and the second step of performing nuclear hydrogenation of an aromatic bicyclic or higher ring at a lower reaction temperature, There has been proposed a hydrotreating method for obtaining a feedstock for FCC by hydrotreating light oil or atmospheric residue oil.

  Patent Document 3 proposes a method for improving desulfurization activity and denitrogenation activity using a catalyst containing phosphorus.

  However, in an actual direct desulfurization apparatus, in order to obtain a desired desulfurized product oil, an operation is performed in which the sulfur content of the product oil is constant, and unless a catalyst having only improved denitrogenation activity is used, The nitrogen content of was not reduced. Therefore, even if a hydrotreating catalyst having improved desulfurization activity and denitrogenation activity by the method as described above is used, the nitrogen content in the product oil cannot be reduced in actual operation.

JP-A-8-012978 JP-A-8-183964 JP 2000-351978 A

J. et al. Japan Petrol. Inst. , 23, (2), 110 (1980)

  In view of the above circumstances, a catalyst having high denitrification activity relative to desulfurization activity, so-called high denitrification selectivity, and a hydrotreating method using the same are desired.

  In view of the above-described conventional situation, the present invention provides a method for producing a hydrotreated oil that can efficiently obtain a hydrotreated oil that has been suitably desulfurized and denitrogenated from a heavy hydrocarbon oil as an FCC feedstock. The purpose is to provide. Another object of the present invention is to provide a method for producing a catalytic cracked oil, which can efficiently obtain a catalytic cracked oil by using the hydrotreated oil obtained by the above production method as a feedstock for FCC. To do.

  As a result of earnest research to develop a method for efficiently producing a highly desulfurized and denitrogenated FCC feedstock from heavy hydrocarbon oil, the present inventors have obtained a specific composition and a specific average pore diameter. In order to propose the present invention, it has been discovered that by using a hydrotreating catalyst having a hydrotreating oil suitably desulfurized and denitrogenated as a feedstock for FCC while maintaining an appropriate catalyst life It came.

That is, one aspect of the present invention relates to the following method for producing hydrotreated oil and method for producing catalytic cracked oil.
(1) A step of obtaining a hydroprocessing oil by circulating heavy hydrocarbon oil through a reactor filled with a hydroprocessing catalyst, wherein the hydroprocessing catalyst comprises phosphorus, an iron group element, and a sixth element. The ratio C ₂ / C ₁ of the content C ₂ of the iron group element to the content C ₁ of phosphorus in the hydroprocessing catalyst containing a group element is less than 0.60 in molar ratio, and the hydroprocessing A method for producing a hydrotreated oil, wherein the average pore diameter of the catalyst is larger than 7.5 nm and smaller than 9.5 nm.
(2) In the hydrotreating catalyst, the ratio C ₂ / C ₃ of the content C ₂ of the iron group element to the content C ₃ of the group 6 element is less than 0.45 in molar ratio, and the group 6 The production method according to (1), wherein the ratio C ₁ / C ₃ of the phosphorus content C _{1 to} the element content C ₃ is more than 0.23 in terms of molar ratio.
(3) Catalytic cracking comprising: a step of obtaining hydrotreated oil by the production method according to (1) or (2) above; and a step of obtaining catalytic cracked oil by fluid catalytic cracking of the hydrotreated oil. Oil production method.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the hydroprocessing oil which can obtain efficiently the hydroprocessing oil desulfurized and denitrogenated suitably as a FCC feedstock from heavy hydrocarbon oil is provided. Moreover, according to this invention, the manufacturing method of catalytic cracking oil which can obtain catalytic cracking oil efficiently is provided.

  A preferred embodiment of the present invention will be described below.

  The manufacturing method of the hydroprocessing oil which concerns on this embodiment is equipped with the process of distribute | circulating heavy hydrocarbon oil to the reactor with which the hydroprocessing catalyst was filled, and obtaining hydroprocessing oil.

  In the present embodiment, the hydrotreating catalyst contains phosphorus, an iron group element, and a group 6 element. In this specification, the iron group element indicates a metal element belonging to the elements of Group 8, 9 and 10 of the fourth period of the periodic table, and the Group 6 element indicates a Group 6 element of the periodic table. The metal element which belongs to is shown. Examples of the iron group element include iron (Fe), cobalt (Co), and nickel (Ni), and examples of the group 6 element include chromium (Cr), molybdenum (Mo), and tungsten (W).

In the present embodiment, the ratio C ₂ / C ₁ (molar ratio) of the iron group element content C _{2 to} the phosphorus content C ₁ in the hydrotreating catalyst is less than 0.60. Moreover, the average pore diameter of the hydrotreating catalyst is larger than 7.5 nm and smaller than 9.5 nm.

  In the production method according to the present embodiment, a hydrotreated oil that is suitably desulfurized and denitrogenated as a raw material oil for FCC from heavy hydrocarbon oil can be efficiently obtained.

  In this embodiment, since the hydrotreating catalyst has a specific metal composition and a specific average pore diameter, a good catalyst life and excellent denitrification activity can be obtained in the hydrotreating of heavy hydrocarbons. For this reason, according to the production method according to the present embodiment, even in the operation in which the generated oil sulfur content is constant as in the prior art, denitrification proceeds efficiently in addition to desulfurization, and the nitrogen content is sufficiently reduced. A hydrotreated oil can be obtained. That is, in the production method according to the present embodiment, compared with the conventional direct desulfurization method, the hydrotreated oil that is suitably denitrogenated as the FCC feedstock can be efficiently produced.

<Raw oil>
The feedstock oil used in the method for producing hydrotreated oil according to the present embodiment may be a heavy hydrocarbon oil. In the present specification, heavy hydrocarbon oil means a fraction containing a fraction having a boiling point of 380 ° C. or higher under normal pressure.

  The heavy hydrocarbon oil may be, for example, an atmospheric distillation residue oil, a vacuum distillation residue oil, a solvent de-peeling oil and a visbreaking oil, and the like using these as raw materials. Further, the heavy hydrocarbon oil may contain a vacuum gas oil, a residual oil of a fluid catalytic cracking device, and the like.

  The solvent-peeling oil may be, for example, a heavy hydrocarbon oil having a boiling point of 550 ° C. or more and a fraction content of 70% by mass or more.

  The method for producing the solvent removal oil is not particularly limited. For example, the solvent removal oil can be obtained by solvent removal using a chain saturated hydrocarbon having 3 to 6 carbon atoms as a solvent. Specific examples of the solvent include propane, normal butane, isobutane, normal pentane, isopentane, and normal hexane. One or more of these may be used as the solvent. Further, as the solvent in solvent removal, a solvent containing 50% by volume or more of a chain saturated hydrocarbon having 5 or 6 carbon atoms is preferably used. According to such a solvent, 60% by volume or more, or 70% by volume. There is a tendency that a solvent-peeling oil is obtained at a high extraction rate of at least%. In addition, the residue after extraction is isolate | separated as a part for pitch.

  The heavy hydrocarbon oil used as the raw material oil preferably has a sulfur content of 5.0% by mass or less, and more preferably 4.0% by mass or less. If the sulfur content is within this range, the content of sulfur in the resulting hydrotreated oil is sufficiently reduced, and the content of sulfur in the catalytic cracked oil obtained thereafter is also suitable. Reduced. In addition, the lower limit of the sulfur content in the heavy hydrocarbon oil is not particularly limited, but may be, for example, 0.6% by mass or more and 0.8% by mass or more. According to the production method according to the present embodiment, even when a heavy hydrocarbon oil having such a sulfur content is used as a raw material oil, the sulfur in the hydrotreated oil is sufficiently desulfurized by hydrotreating. The content of min is sufficiently reduced.

  The content of nitrogen in the heavy hydrocarbon oil may be, for example, 0.05% by mass or more, and may be 0.07% by mass or more. In the production method according to the present embodiment, since the hydrotreating catalyst has an excellent denitrification activity, even when a heavy hydrocarbon oil containing a nitrogen content is used as a raw material oil as described above, the hydrotreating treatment is sufficiently performed. It is denitrified and the nitrogen content in the hydrotreated oil is sufficiently reduced. Moreover, content of the nitrogen content in heavy hydrocarbon oil may be 0.35 mass% or less, for example, and may be 0.30 mass% or less. When the nitrogen content is within this range, the nitrogen content in the resulting hydrotreated oil tends to be more significantly reduced.

  In heavy hydrocarbon oil, content of basic nitrogen content may be 0.02 mass% or more, for example, and may be 0.03 mass% or more. In the production method according to the present embodiment, since the hydrotreating catalyst has excellent denitrification activity, even when a heavy hydrocarbon oil containing a basic nitrogen content is used as a raw material oil in this way, It is sufficiently denitrified, and the content of basic nitrogen in the hydrotreated oil is sufficiently reduced. Moreover, content of the basic nitrogen content in heavy hydrocarbon oil may be 0.12 mass% or less, for example, and may be 0.10 mass% or less. If content of basic nitrogen content is this range, there exists a tendency for the basic nitrogen content in the hydrotreated oil obtained to be reduced notably.

  The heavy hydrocarbon oil may contain heavy metals such as nickel and vanadium. The heavy metal content of the heavy hydrocarbon oil is preferably, for example, 200 ppm by mass or less, and more preferably 100 ppm by mass or less. If it is such content, the fall of the catalyst life of the hydroprocessing catalyst by metal poisoning can fully be suppressed.

  Moreover, in heavy hydrocarbon oil, content of heavy metal may be more than 3 mass ppm, and may be 5 mass ppm or more. Even when heavy hydrocarbon oil containing heavy metal is used as a raw material oil, it is possible to sufficiently suppress a decrease in the catalyst life of the hydrotreating catalyst by filling the demetallization catalyst upstream of the reactor. . In addition, content of the heavy metal in the heavy hydrocarbon oil after metal removal may be 12 mass ppm or less, for example, and may be 15 mass ppm or less.

  The heavy hydrocarbon oil may contain asphaltenes. The content of asphaltenes in the heavy hydrocarbon oil may be, for example, 0.05% by mass or more, and may be 2.0% by mass or more. Moreover, content of the asphaltene content in heavy hydrocarbon oil may be 3.0 mass% or less, for example, and may be 4.0 mass% or less.

  In the present specification, the content of sulfur in heavy hydrocarbon oil is a value determined in accordance with JIS K2541 “Crude oil and petroleum products / sulfur content test method”. The nitrogen content in the heavy hydrocarbon oil is a value determined in accordance with JIS K2541 “Crude oil and petroleum products / nitrogen content test method”. In addition, the content of basic nitrogen in heavy hydrocarbon oil is determined by UOP test method No. The value measured based on 269-90 is shown. The heavy metal content in the heavy hydrocarbon oil indicates a value measured by fluorescent X-ray analysis. Further, the content of asphaltenes in the heavy hydrocarbon oil indicates a value measured in accordance with IP143 as a heptane-insoluble component.

<Hydroprocessing catalyst>
The hydrotreatment catalyst contains phosphorus, an iron group element, and a group 6 element, and the ratio C ₂ / C ₁ (molar ratio) of the content C ₂ of the iron group element to the content C ₁ of phosphorus in the hydrotreatment catalyst ) Is less than 0.60. Moreover, the average pore diameter of the hydrotreating catalyst is larger than 7.5 nm and smaller than 9.5 nm.

  The hydrotreating catalyst may include an inorganic oxide support and an active component supported on the inorganic oxide support. At this time, an active ingredient contains phosphorus, an iron group element, and a 6th group element.

  As the inorganic oxide carrier, a refractory inorganic oxide carrier is suitable. For example, alumina, silica, titania, magnesia, zirconia, boron oxide, zinc oxide, zeolite (for example, Y zeolite, ZSM-5 zeolite, etc.), And mixtures thereof.

  The active component carried on the inorganic oxide carrier may contain components other than phosphorus, iron group elements, and Group 6 elements, and may contain, for example, platinum.

  The hydrotreating catalyst preferably contains cobalt and / or nickel as the iron group element, and more preferably contains nickel.

  The hydrotreating catalyst preferably contains molybdenum and / or tungsten as the Group 6 metal, and more preferably contains molybdenum.

  The phosphorus content in the hydrotreating catalyst may be, for example, 0.1% by mass or more, and preferably 1.0% by mass or more. Moreover, phosphorus content may be 4.0 mass% or less, for example, and it is preferable that it is 3.0 mass% or less.

  The content of the iron group element in the hydrotreating catalyst may be, for example, 1.0% by mass or more, and preferably 1.5% by mass or more. Moreover, content of an iron group element may be 3.5 mass% or less, for example, and it is preferable that it is 3.0 mass% or less.

  The content of the Group 6 element in the hydrotreating catalyst may be, for example, 5.0% by mass or more, and preferably 6.0% by mass or more. In addition, the content of the Group 6 element may be, for example, 12.0% by mass or less, and preferably 11.0% by mass or less.

  In addition, in this specification, content of phosphorus, an iron group element, and a 6th group element shows the value measured by ICP emission spectroscopy.

In the hydrotreating catalyst, the ratio C ₂ / C ₁ (molar ratio) of the iron group element content C _{2 to} the phosphorus content C ₁ is less than 0.60, preferably less than 0.55, More preferably, it is less than 0.53. Such a hydrotreating catalyst tends to further improve the denitrification activity. Further, the ratio C ₂ / C ₁ is preferably 0.20 or more, and more preferably 0.25 or more. According to the hydrotreating catalyst having such a ratio C ₂ / C ₁ , the desulfurization activity tends to be further improved.

In the hydrotreating catalyst, the ratio C ₁ / C ₃ (molar ratio) of the phosphorus content C _{1 to} the Group C element content C ₃ is preferably more than 0.23 and more than 0.40. Is more preferable, and it is further more preferable that it is more than 0.50. Such a hydrotreating catalyst tends to further improve the denitrification activity. The ratio _C 1 / _{C 3} is preferably less than 1.5, more preferably less than 1.0. Such a hydrotreating catalyst tends to further improve metal resistance.

In the hydrotreating catalyst, the ratio C ₂ / C ₃ (molar ratio) of the content C ₂ of the iron group element to the content C ₃ of the group 6 element is preferably less than 0.45, 0.44 More preferably, it is more preferably less than 0.42. In such a hydrotreating catalyst, the ratio of denitrification activity to desulfurization activity (denitrogen selectivity) is further increased, and a highly denitrogenated hydrotreated oil tends to be obtained more easily.

  The average pore diameter of the hydrotreating catalyst is larger than 7.5 nm, preferably larger than 7.6 nm, and more preferably larger than 7.8 nm. In such a hydrotreating catalyst, the catalyst life tends to be remarkably improved by improving the metal resistance performance.

  Moreover, the average pore diameter of the hydrotreating catalyst is less than 9.5 nm, preferably less than 9.2 nm, and more preferably less than 9.0 nm. In such a hydrotreating catalyst, the denitrification selectivity is further improved, and a highly denitrogenated hydrotreating oil tends to be obtained more easily.

  In the present specification, the average pore diameter of the hydrotreating catalyst indicates a value measured by a nitrogen adsorption method.

The specific surface area of the hydrotreating catalyst is preferably 150 m ² / g or more, more preferably 200 m ² / g or more, preferably 350 m ² / g or less, more preferably 320 m ² / g or less. Such a hydrotreating catalyst tends to provide a more excellent denitrification activity together with sufficient desulfurization performance.

  As the hydrotreating catalyst, a new catalyst, a regenerated catalyst or the like can be used without particular limitation.

<Demetallation catalyst>
In the method for producing hydrotreated oil according to the present embodiment, the reactor may be further filled with a catalyst other than the hydrotreated catalyst. For example, when the heavy hydrocarbon oil used as the raw material oil contains heavy metals, the reactor may be filled with a demetallation catalyst upstream of the hydrotreating catalyst. That is, the reactor may be a reactor in which the demetalization catalyst is filled in the front stage and the hydrotreatment catalyst is filled in the back stage.

  The demetallation catalyst is not particularly limited as long as it can remove at least part of the heavy metal in the heavy hydrocarbon oil.

  A suitable example of the demetallation catalyst includes an inorganic oxide carrier and an active component supported on the inorganic oxide carrier. As the inorganic oxide carrier, a refractory inorganic oxide carrier is preferable, and examples thereof include alumina, silica, alumina-silica, boron oxide, zinc oxide, and a mixture thereof. In addition, examples of the active component include Group 6 elements such as molybdenum and tungsten, and iron group elements such as cobalt and nickel. Further, the inorganic oxide carrier may further contain phosphorus.

  In the metal removal catalyst, the average pore diameter measured by the nitrogen adsorption method is preferably 10 nm or more, more preferably 12 nm or more. With such a demetallization catalyst, there is a tendency that a superior demetallization activity can be obtained. Further, the average pore diameter of the demetallation catalyst is preferably 25 nm or less, more preferably 23 nm or less. With such a demetallation catalyst, there is a tendency that more excellent hydrotreating activity and catalyst strength can be obtained.

  The pore volume of the demetallation catalyst is preferably 0.6 mL / g or more, more preferably 0.65 mL / g or more, preferably 1.0 mL / g or less, more preferably 0.9 mL / g or less. . With such a demetallation catalyst, sufficient catalyst life and catalyst strength are obtained, and there is a tendency that operation can be performed more stably.

  As the metal removal catalyst, a new catalyst, a regenerated catalyst or the like can be used without particular limitation. Moreover, the filling rate of the demetallization catalyst in the reactor can be appropriately changed according to the operating conditions and the feedstock composition.

  The reactor may be further filled with a catalyst other than the demetallation catalyst and the hydrotreating catalyst, and may be further filled with, for example, a middle stage catalyst having both demetallation activity and desulfurization activity. As such a catalyst, various known catalysts can be used.

<Reaction conditions>
In the method for producing hydrotreated oil according to this embodiment, heavy hydrocarbon oil is circulated through a reactor filled with a hydrotreating catalyst, and hydrogenation treatment of the heavy hydrocarbon oil is performed. Chemically treated oil is obtained.

  The reaction conditions for the hydrotreatment may be adjusted as appropriate according to the target product oil composition (for example, the sulfur content) and the catalytic activity of the catalyst charged in the reactor.

  For example, the reaction temperature of the hydrotreatment may be 300 ° C. or higher and may be 350 ° C. or higher. By setting it as such reaction temperature, there exists a tendency for the activity of the hydrotreating catalyst with which the reactor was filled to be exhibited more notably. Moreover, the reaction temperature of the hydrogenation treatment may be, for example, 500 ° C. or lower, and may be 450 ° C. or lower. By setting such a reaction temperature, the thermal decomposition of the heavy hydrocarbon oil does not proceed excessively, the operation of the hydroprocessing apparatus can be performed smoothly, and the deterioration of the activity of the hydroprocessing catalyst is suppressed. it can.

  The hydrogen partial pressure in the hydrogenation treatment may be, for example, 3 MPa or more, or 5 MPa or more. By setting it as such a hydrogen partial pressure, there exists a tendency for hydrogenation reaction to fully advance and to obtain the hydrotreated oil by which desulfurization and denitrogenation were carried out more highly. Moreover, the hydrogen partial pressure in the hydrogenation treatment may be, for example, 25 MPa or less, or 20 Mpa or less. Such a hydrogen partial pressure tends to be economically advantageous because an increase in equipment construction costs and operating costs can be avoided.

  The hydrogen / oil ratio in the hydrotreatment may be, for example, 400 L / L or 500 L / L. With such a hydrogen / oil ratio, the hydrogenation activity of the hydrotreating catalyst tends to be more prominently exhibited. In addition, the hydrogen / oil ratio in the hydrotreatment may be, for example, 3000 L / L or 1800 L / L. By setting such a hydrogen / oil ratio, excellent economic efficiency can be ensured.

Liquid hourly space velocity in the hydrogenation process (LHSV) may be for example 0.1 h ^-1 or more, may be at 0.2 h ^-1 or more. By setting it as such liquid space velocity, the outstanding economical efficiency is securable. The liquid hourly space velocity in the hydrogenation process can be, for example, a 3.0 h ^-1, may be 2.0 h ^-1. By setting it as such a liquid space velocity, there exists a tendency to obtain the hydrotreated oil desulfurized and denitrogenated more highly.

<Hydrotreated oil>
The hydrotreated oil obtained by the method for producing hydrotreated oil according to this embodiment is highly desulfurized and denitrogenated, and can be suitably used as a FCC feedstock.

  The content of sulfur in the hydrotreated oil is preferably 0.15% by mass or less, more preferably 0.10% by mass or less, and further preferably 0.05% by mass or less. .

  The nitrogen content in the hydrotreated oil is preferably 0.15% by mass or less, and more preferably 0.13% by mass or less. Moreover, it is preferable that content of basic nitrogen content is 0.05 mass% or less, and it is more preferable that it is 0.04 mass% or less.

  The contents of nickel and vanadium in the hydrotreated oil are each preferably 10 ppm or less, and more preferably 5 ppm or less. Such hydrotreated oil can sufficiently suppress metal poisoning of the catalyst used in the FCC process.

  According to the manufacturing method which concerns on this embodiment, the hydroprocessing oil suitable for a FCC process can be manufactured stably by the method excellent in economical efficiency.

<FCC process>
In the present embodiment, catalytically cracked oil can be obtained efficiently by using the hydrotreated oil obtained by the above-described production method as the FCC feedstock. That is, the method for producing catalytic cracking oil according to the present embodiment includes a step of obtaining hydrotreated oil by the above-described method and a step of obtaining catalytic cracked oil by fluid catalytic cracking of hydrotreated oil. It's okay.

  In the method for producing catalytic cracking oil according to the present embodiment, since the hydrotreated oil obtained by the above-described production method is suitably denitrified as a feedstock for FCC, catalyst deterioration in fluid catalytic cracking is sufficient. Therefore, the catalytic cracking oil can be obtained efficiently.

  In this embodiment, the mode of fluid catalytic cracking is not particularly limited, and can be carried out by a known method.

  The catalytic cracked oil obtained by the production method according to the present embodiment can be suitably used for gasoline fractions, light oil fractions, coke raw materials, chemical raw materials such as propylene and butadiene, and the like.

  The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment.

  Next, although an example and a comparative example explain the present invention, the present invention is not limited by these examples.

<Preparation of raw oil>
In the following Examples and Comparative Examples, an oil mixed with an equal volume of normal pressure residue oil A and solvent degreasing oil having the following composition was used as a raw material oil.

(Normal pressure residual oil A)
Sulfur content in atmospheric residue: 2.9% by mass
Vanadium content in the atmospheric residue: 40 ppm by mass
Nickel content in atmospheric residue: 15 ppm by mass
Asphaltene content in atmospheric residue oil: 3.0% by mass
Density of atmospheric residue at 15 ° C .: 0.9619 g / cm ³
Kinematic viscosity of atmospheric residue at 100 ° C .: 30.5 mm ² / s
Carbon residue content in atmospheric residue oil: 9.0% by mass
Nitrogen content in atmospheric residue: 0.154% by mass
Basic nitrogen content in atmospheric residue oil: 0.052% by mass

(Solvent removal oil)
As the solvent deasphalted oil, the following depressurized residual oil was used which was desolvated with a 70% extraction rate using a hydrocarbon solvent containing 90% or more of hydrocarbons having 5 and 6 carbon atoms. The properties of the solvent-peeling oil were as follows.
Sulfur content in vacuum residue oil: 4.4% by mass
Vanadium content in vacuum residue oil: 98 ppm by mass
Nickel content in vacuum residue oil: 30 ppm by mass
Content of asphaltene in vacuum residue oil: 10.4% by mass
Density of vacuum residue oil at 15 ° C .: 1.0400 g / cm ³
Kinematic viscosity of vacuum residue oil at 100 ° C .: 461 mm ² / s
Residual carbon content in vacuum residue oil: 24.7% by mass
Nitrogen content in the vacuum residue oil: 0.38% by mass
Basic nitrogen content in the vacuum residue oil: 0.13% by mass
Content of sulfur in solvent-peeling oil: 4.2% by mass
Vanadium content in solvent-desorbed oil: 29 mass ppm
Content of nickel in solvent-peeling oil: 9 mass ppm
Content of asphaltene in solvent-peeling oil: 0.2% by mass
Density of solvent removal oil at 15 ° C .: 1.0037 g / cm ³
Kinematic viscosity of solvent removal oil at 100 ° C .: 419 mm ² / s
Residual carbon content in solvent removal oil: 15.5% by mass
Nitrogen content in solvent-peeling oil: 0.182% by mass
Content of basic nitrogen in solvent-peeling oil: 0.062% by mass

<Example 1>
In Example 1, as a demetallation catalyst, a catalyst (demetallization catalyst X) in which molybdenum is supported on an alumina carrier at 2.7% by mass (in terms of molybdenum element) (average pore diameter: 18 nm, pore volume: 0.87 mL / g) was used. Moreover, the catalyst A having the composition shown in Table 1 was used as the hydrotreating catalyst. In Table _1, C 2 / _{C 3} indicates the ratio of the content _{C 2} of the iron group element to the content _{C 3} of Group 6 _elements, C 1 / _{C 3,} the content of the group 6 element shows a phosphorus ratio of content _{C 1} of for C _3, C 2 / _{C 1} represents the ratio of the content _{C 2} of the iron group element to the content _{C 1} of phosphorus.

The metal removal catalyst X was filled on the reactor inlet side of the hydrotreating apparatus, and an equal volume of catalyst A was filled on the subsequent stage side. Using this hydrotreating apparatus, hydrotreating was performed under the following conditions.
Hydrogen partial pressure: 14.4 Mpa
Hydrogen / oil ratio: 1000L / L
LHSV: 0.44h ^-1

  The reaction temperature was changed to 360 ° C., 380 ° C. and 400 ° C., and the hydrotreated oil obtained under each condition was analyzed for sulfur content, nitrogen content and heavy metal, and based on the analysis results, desulfurization activity (kHDS) , Denitrification activity (kHDN), and demetallation activity (kHDM) were determined. Each activity is a reaction order, a desulfurization reaction is secondary, a denitrogenation reaction is primary, and a demetallation reaction is primary, and a reaction rate constant at each reaction temperature is calculated. It was calculated as an average value.

  Further, the basic nitrogen removal rate was calculated from the basic nitrogen concentration in the raw material oil and the basic nitrogen concentration in the hydrotreated oil at a reaction temperature of 380 ° C. The ratio of denitrification activity to desulfurization activity (kHDN / kHDS) was defined as HDN selectivity. Further, as an indicator of the catalyst life of the hydrotreating catalyst, the time until the activity was reduced to 20% with respect to the initial desulfurization activity was measured, and a relative value with respect to Comparative Example 4 described later was obtained, and this was determined as the relative metal resistance. It was.

  Table 2 shows the desulfurization activity (kHDS), denitrification activity (kHDN), demetallation activity (kHDM), basic nitrogen removal rate, HDN selectivity, and relative metal resistance determined by the above method.

<Examples 2 to 4>
The hydrotreating and the obtained hydrotreating oil were analyzed in the same manner as in Example 1, except that the catalysts B to D shown in Table 1 were used instead of the catalyst A as the hydrotreating catalyst. . The analysis results were as shown in Table 2.

<Comparative Examples 1-4>
The hydrotreating and the obtained hydrotreating oil were analyzed in the same manner as in Example 1 except that the catalysts E to H shown in Table 1 were used instead of the catalyst A as the hydrotreating catalyst. . The analysis results were as shown in Table 2.

  When Examples and Comparative Examples were compared, in the Examples, high denitrification selectivity and basic nitrogen removal rate were obtained while suppressing a significant decrease in catalyst life (relative metal resistance).

<Example 5>
A hydroprocessing system using a plurality of catalysts was implemented to obtain a product oil. Moreover, in order to confirm the reactivity of the catalytic cracking reaction of the obtained product oil, a MAT (Micro Activity Test) test was performed on the product oil. Details will be described below.

  First, the demetallation catalyst X, a demetallation catalyst Y (average pore diameter of 18 nm, pore volume) in which 6 mass% of molybdenum (in terms of molybdenum element) and 1.5 mass% of nickel (in terms of nickel element) are supported on an alumina carrier. 0.80 mL / g), the desulfurization catalyst E, the desulfurization catalyst H, and the desulfurization catalyst A were prepared. Moreover, what mixed the said solvent debris oil and the normal pressure residual oil B shown below by 54:46 (volume ratio) was prepared as raw material oil for hydroprocessing.

(Normal pressure residual oil B)
Sulfur content in atmospheric residual oil: 0.92% by mass
Vanadium content in atmospheric residue: 11 mass ppm
Nickel content in atmospheric residue: 11 ppm by mass
Asphaltene content in atmospheric residue: 0.2% by mass
Density of atmospheric residue at 15 ° C .: 0.9187 g / cm ³
Kinematic viscosity of atmospheric residual oil at 100 ° C .: 25.2 mm ² / s
Carbon residue content in atmospheric residual oil: 5.1% by mass
Nitrogen content in atmospheric residue: 0.170% by mass
Basic nitrogen content in atmospheric residue: 0.057% by mass

A reactor connected to two reactors is prepared. The first column is filled with the demetallation catalyst X and the demetalization catalyst Y in this order from the inlet side, and the second column is filled with the desulfurization catalyst E and desulfurization from the inlet side. Catalyst H and desulfurization catalyst A were charged in this order. The amount of catalyst used was X: Y: E: H: A = 3: 41: 11: 12: 33 (volume ratio). Using this reactor, the hydrogenation treatment was carried out under the following conditions. The first column inlet temperature was 350 ° C. for 30 days from the start of the reaction.
Hydrogen partial pressure: 14.4 Mpa
Hydrogen / oil ratio: 1000L / L
LHSV: 0.44h ^-1
1st tower outlet temperature = 1st tower inlet temperature + 8 ° C
Second tower inlet temperature = First tower inlet temperature -2 ° C
2nd tower outlet temperature = 2nd tower inlet temperature + 20 ° C

  30 days after the start of the reaction, the reaction temperature was adjusted so that the sulfur content in the bottom of the product oil (residue in distillation separation, fraction having a boiling point of 390 ° C. or higher) was 0.6% by mass. Was 364 ° C. The fraction of the product oil having a boiling point of less than 390 ° C. was cut to obtain desulfurized oil 5A. The composition of the desulfurized oil 5A was as shown in Table 3. This desulfurized oil 5A was used for the MAT test.

In the MAT test, FCC feedstock A in which the reduced pressure light oil whose composition was shown in Table 3 and the above desulfurized oil 5A were mixed at 57:43 (mass ratio) was used as the feedstock. The MAT test was performed under the following conditions. A commercially available FCC catalyst was used as the catalyst. The test results are shown in Table 4.
Reaction temperature: 530 ° C
Catalyst / oil ratio: 8.5 (weight ratio)
Catalyst weight: 12g

<Comparative Example 5>
The first column of the reactor is filled with the demetalization catalyst X and the demetalization catalyst Y in this order from the inlet side, and the second column is filled with the desulfurization catalyst E and the desulfurization catalyst H in this order from the inlet side. Hydrogenation treatment was performed in the same manner as in Example 5 except that X: Y: E: H = 22: 22: 23: 33 (volume ratio).

  30 days after the start of the reaction, the reaction temperature was adjusted so that the sulfur content in the bottom of the product oil (residue in distillation separation, fraction having a boiling point of 390 ° C. or higher) was 0.6% by mass. Was 377 ° C. The fraction of the product oil having a boiling point of less than 390 ° C. was cut to obtain desulfurized oil 5B. The composition of the desulfurized oil 5B was as shown in Table 3. This desulfurized oil 5B was used for the MAT test.

  In the MAT test, FCC feedstock B obtained by mixing the vacuum gas oil shown in Table 3 and the desulfurized oil 5B at 57:43 (mass ratio) was used as the feedstock. A MAT test was performed in the same manner as in Example 5 except that FCC feedstock B was used as the feedstock. The test results are shown in Table 4.

<Example 6>
The MAT test was conducted in the same manner as in Example 5 except that the catalyst / oil ratio was changed to 9.5 (subsidiary ratio). The test results are shown in Table 4.

  In Table 3, “Density (15 ° C.)” indicates a density at 15 ° C., “LCO fraction” indicates the content of a fraction having a boiling point of 221 ° C. or more and less than 343 ° C., and “VR fraction” is a boiling point. The content of a fraction at 538 ° C. or higher is shown. Further, “residual carbon”, “nitrogen”, “basic nitrogen”, “sulfur”, “Ni” and “V” respectively represent residual carbon, nitrogen, basic nitrogen, sulfur, nickel and The content of vanadium is shown. The “average molecular weight” represents the average molecular weight number of hydrocarbons measured by a GPC apparatus.

  In Table 4, “dry gas”, “LPG”, “WCCG”, “LCO”, “CLO”, and “CAKE” are hydrocarbons having 1 or 2 carbon atoms and hydrocarbons having 3 or 4 carbon atoms, respectively. , Hydrocarbons having a carbon number of 5 or more and a boiling point of less than 221 ° C., hydrocarbons having a boiling point of 221 ° C. or more and less than 343 ° C., liquid hydrocarbons having a boiling point of 343 ° C. or more, and solid products. The “decomposition rate” indicates the ratio of the amount obtained by removing LCO, CLO and coke from the total product.

  As shown in Table 3, in the hydrogenation treatment of Example 5, basic nitrogen was used even though the reaction temperature (364 ° C.) at which the sulfur content was 0.6% by mass was lower than that of Comparative Example 5 (377 ° C.). Is less than that of Comparative Example 5. Moreover, as shown in Table 4, in the catalytic cracking reaction of Example 5, the amount of coke produced is suppressed as compared with Comparative Example 5. Further, as shown in Table 4, in Example 6 in which the catalyst / feed oil ratio was adjusted so that the amount of coke produced was comparable to that in Comparative Example 5, a higher decomposition rate was obtained as compared with Comparative Example 5.

Claims (3)

The heavy hydrocarbon oil is circulated through a reactor filled with a hydroprocessing catalyst to obtain a hydroprocessing oil,
The hydrotreating catalyst contains phosphorus, an iron group element, and a group 6 element;
The ratio C ₂ / C ₁ of the iron group element content C _{2 to} the phosphorus content C ₁ in the hydroprocessing catalyst is less than 0.60 in molar ratio,
An average pore diameter of the hydrotreating catalyst is larger than 7.5 nm and smaller than 9.5 nm;
A method for producing hydrotreated oil. In the hydrotreating catalyst,
The ratio C ₂ / C ₃ of the content C ₂ of the iron group element to the content C ₃ of the group 6 element is less than 0.45 in molar ratio,
The ratio _C 1 / _{C 3} content _{C 1} of phosphorus to the content _{C 3} of group 6 element is greater than 0.23 in molar ratio,
The manufacturing method according to claim 1. Obtaining a hydrotreated oil by the production method according to claim 1 or 2,
Obtaining hydrocracked oil by fluid catalytic cracking of the hydrotreated oil;
A process for producing catalytic cracking oil.