JP6770953B2 - Method for producing hydrotreated oil and method for producing catalytically cracked oil - Google Patents

Description

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

Until now, at refineries in Japan, fluid cracking (FCC) equipment has played a central role in gasoline production in order to meet gasoline demand and promote the weight reduction of heavy hydrocarbon oils. Further, in recent years, there has been a great deal of interest in FCC equipment as a process for producing high-value-added light hydrocarbon oil from heavy hydrocarbon oil, and in pursuit of higher economic efficiency, conventional reduced-pressure light oil distiller as a raw material oil for FCC. In addition to the oil, raw material oil mixed with residual oil such as atmospheric residue residue is also used.

Since the atmospheric 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 device, which is the pretreatment of the FCC device, and the reaction is carried out under high temperature and high pressure conditions. It is demetallized, desulfurized and denitrified.

By the way, zeolite is generally used as the FCC catalyst used in the FCC apparatus, and it has been desired to reduce the nitrogen content that poisons zeolite, particularly the basic nitrogen content, in the raw material oil for FCC. That is, it is considered that if the nitrogen content in the raw material oil for FCC can be reduced, the performance of the FCC catalyst will be sufficiently exhibited and the efficiency of gasoline production will be improved. However, until now, it has been considered that if the desulfurization reaction proceeds in the direct desulfurization apparatus for heavy hydrocarbon oil, the denitrification reaction also proceeds, and there has been no particular technique for improving the denitrification activity.

Although it is desired to reduce the nitrogen content of heavy hydrocarbon oils, it has been considered that the main purpose has been to reduce the sulfur content, and the desulfurization catalyst that removes the sulfur content is protected. Attention has continued to be paid to the development of demetallization catalysts, which play a role.

For example, in Non-Patent Document 1, by impregnating and supporting phosphorus, desulfurization activity and denitrification activity are improved, but the catalyst pore volume is reduced, causing rapid metal poisoning and shortening the catalyst life. It is stated that there is a tendency.

So far, many reports have been made on hydrogenation treatment methods for FCC raw material oils. For example, Patent Documents 1 and 2 describe decompression by a first step of performing desulfurization and denitrification treatment at a relatively high reaction temperature and a second step of performing nuclear hydrogenation of two or more aromatic rings at a lower reaction temperature. A hydrogenation treatment method has been proposed in which light oil, atmospheric residual oil, or the like is hydrogenated to obtain a raw material oil for FCC.

Further, Patent Document 3 proposes a method for improving desulfurization activity and denitrification activity by using a catalyst containing phosphorus.

However, in an actual direct desulfurization apparatus, in order to obtain a desired desulfurization product oil, the sulfur content of the product oil is kept constant, and unless a catalyst having only improved denitrification activity is used, the product oil is contained. Nitrogen content was not reduced. Therefore, even if a hydrogenation catalyst having improved desulfurization activity and denitrification activity was used by the above method, the nitrogen content in the produced oil could not be reduced in actual operation.

Japanese Unexamined Patent Publication No. 8-012978 Japanese Unexamined Patent Publication No. 8-183964 Japanese Unexamined Patent Publication No. 2000-351978

J. Japan Peterl. Inst. , 23, (2), 110 (1980)

From the above circumstances, a catalyst having high denitrification activity with respect to desulfurization activity, that is, a catalyst having high denitrification selectivity, and a hydrogenation treatment method using the same are desired.

In view of the above-mentioned conventional situation, the present invention provides a method for producing a hydrogenated oil, which can efficiently obtain a desulfurized and denitrified hydrogenated oil as a raw material oil for FCC from a heavy hydrocarbon oil. The purpose is to provide. Another object of the present invention is to provide a method for producing a catalytic cracking oil, which can efficiently obtain a catalytic cracking oil by using the hydrotreated oil obtained by the above production method as a raw material oil for FCC. To do.

As a result of diligent research to develop a method for efficiently producing a highly desulfurized and denitrified feedstock oil for FCC from heavy hydrocarbon oil, the present inventors have obtained a specific composition and a specific average pore size. We have discovered that by using a hydrogenated catalyst having a hydrogenated catalyst, it is possible to produce a hydrotreated oil suitably desulfurized and denitrified as a raw material oil for FCC while maintaining an appropriate catalyst life, and propose the present invention. I arrived.

That is, one aspect of the present invention relates to the following method for producing hydrotreated oil and the method for producing catalytically cracked oil.
(1) A step of passing a heavy hydrocarbon oil through a reactor filled with a hydrogenation treatment catalyst to obtain a hydrogenation treatment oil is provided, and the hydrogenation treatment catalyst is phosphorus, an iron group element, and a sixth. The ratio C ₂ / C ₁ of the iron group element content C _{2 to} the phosphorus content C ₁ in the hydrogenation catalyst containing a group element is less than 0.60 in terms of molar ratio, and the hydrogenation treatment. 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 hydrogenation treatment 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 terms of molar ratio, and the group 6 element. The production method according to (1) above, 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) Contact cracking comprising a step of obtaining a hydrocracked oil by the production method according to the above (1) or (2) and a step of obtaining a catalytic cracking oil by fluid cracking of the hydrocracked oil. How to make oil.

According to the present invention, there is provided a method for producing a hydrotreated oil, which can efficiently obtain a desulfurized and denitrified hydrotreated oil from a heavy hydrocarbon oil as a raw material oil for FCC. Further, according to the present invention, there is provided a method for producing a catalytic cracking oil, which can efficiently obtain a catalytic cracking oil.

Suitable embodiments of the present invention will be described below.

The method for producing a hydrotreated oil according to the present embodiment includes a step of circulating a heavy hydrocarbon oil through a reactor filled with a hydrotreated catalyst to obtain a hydrotreated oil.

In the present embodiment, the hydrogenation catalyst contains phosphorus, an iron group element and a group 6 element. In the present specification, the iron group element indicates a metal element belonging to the elements of groups 8, 9 and 10 of the 4th cycle of the periodic table, and the group 6 element is a group 6 element of the periodic table. Indicates a metal element belonging to. Examples of the group 6 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 hydrogenation catalyst is less than 0.60. The average pore size of the hydrogenation 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 suitably desulfurized and denitrified as a raw material oil for FCC can be efficiently obtained from a heavy hydrocarbon oil.

In the present embodiment, since the hydrogenation catalyst has a specific metal composition and a specific average pore size, good catalyst life and excellent denitrification activity can be obtained in the hydrogenation treatment of heavy hydrocarbons. Therefore, according to the production method according to the present embodiment, denitrification proceeds efficiently in addition to desulfurization even in the conventional operation in which the produced oil sulfur content is constant, and the nitrogen content is sufficiently reduced. Hydrotreated oil can be obtained. That is, in the production method according to the present embodiment, a hydrotreated oil preferably denitrified as a raw material oil for FCC can be efficiently produced as compared with the conventional direct desulfurization method.

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

The heavy hydrocarbon oil may be, for example, atmospheric distillation residual oil, vacuum distillation residual oil, solvent-removing oil and bisbraking oil made from these as raw materials. Further, the heavy hydrocarbon oil may contain reduced pressure light oil, residual oil of a fluid cracking apparatus, and the like.

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

The method for producing the solvent-removing oil is not particularly limited, and for example, it can be obtained by solvent-removing 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. As the solvent, one or more of these may be used. Further, as the solvent for removing the solvent, a solvent containing 50% by volume or more of chain saturated hydrocarbon having 5 or 6 carbon atoms is preferably used, and according to such a solvent, 60% by volume or more or 70% by volume is used. Solvent-free oil tends to be obtained with a high extraction rate of% or more. The residue after extraction is separated as a pitch component.

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. When the sulfur content is within this range, the sulfur content in the obtained hydrotreated oil is sufficiently reduced, and the sulfur content in the subsequently obtained catalytic cracking oil is also preferably. It will be reduced. 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, or 0.8% by mass or more. According to the production method according to the present embodiment, even when such a heavy hydrocarbon oil having a sulfur content is used as a raw material oil, it is sufficiently desulfurized by the hydrogenation treatment and the sulfur in the hydrotreated oil is sufficiently desulfurized. The content of the component is sufficiently reduced.

The nitrogen content 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 hydrogenation treatment catalyst has excellent denitrification activity, even when a heavy hydrocarbon oil containing nitrogen is used as a raw material oil in this way, the hydrogenation treatment is sufficient. It is denitrified and the nitrogen content in the hydrotreated oil is sufficiently reduced. The nitrogen content of the heavy hydrocarbon oil may be, for example, 0.35% by mass or less, and may be 0.30% by mass or less. When the nitrogen content is in this range, the nitrogen content in the obtained hydrotreated oil tends to be reduced more remarkably.

In the heavy hydrocarbon oil, the content of the basic nitrogen content may be, for example, 0.02% by mass or more, and may be 0.03% by mass or more. In the production method according to the present embodiment, since the hydrogenation treatment catalyst has excellent denitrification activity, even when a heavy hydrocarbon oil containing basic nitrogen is used as a raw material oil in this way, the hydrogenation treatment is performed. It is sufficiently denitrified and the content of basic nitrogen in the hydrocarbonated oil is sufficiently reduced. Further, the content of the basic nitrogen content in the heavy hydrocarbon oil may be, for example, 0.12% by mass or less, and may be 0.10% by mass or less. When the content of the basic nitrogen content is within this range, the basic nitrogen content in the obtained hydrotreated oil tends to be reduced more remarkably.

The heavy hydrocarbon oil may contain heavy metals such as nickel and vanadium. The heavy metal content of the heavy hydrocarbon oil is, for example, preferably 200 mass ppm or less, and more preferably 100 mass ppm or less. With such a content, it is possible to sufficiently suppress a decrease in the catalyst life of the hydrogenation treatment catalyst due to metal poisoning.

Further, in the heavy hydrocarbon oil, the content of heavy metal may be more than 3 mass ppm or 5 mass ppm or more. Even when a heavy hydrocarbon oil containing a heavy metal is used as a raw material oil, it is possible to sufficiently suppress a decrease in the catalyst life of the hydrogenation treatment catalyst by filling the upstream side of the reactor with a demetallizing catalyst. .. The content of heavy metals in the heavy hydrocarbon oil after demetallization may be, for example, 12 mass ppm or less, or 15 mass ppm or less.

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

In the present specification, the sulfur content in the heavy hydrocarbon oil indicates a value obtained in accordance with JIS K2541 “Crude oil and petroleum products / sulfur content test method”. The nitrogen content of the heavy hydrocarbon oil indicates a value obtained in accordance with JIS K2541 "Crude oil and petroleum products / nitrogen content test method". The content of basic nitrogen in the heavy hydrocarbon oil was determined by UOP Test Method No. The values measured according to 269-90 are shown. The heavy metal content in the heavy hydrocarbon oil shows the value measured by the fluorescent X-ray analysis method. Moreover, the content of asphaltene content in heavy hydrocarbon oil shows the value measured in accordance with IP143 as the insoluble content of heptane.

<Hydrogenation catalyst>
The hydrogenation catalyst contains phosphorus, an iron group element and a group 6 element, and the ratio of the iron group element content C _{2 to} the phosphorus content C ₁ in the hydrogenation catalyst C ₂ / C ₁ (molar ratio). ) Is less than 0.60. The average pore size of the hydrogenation catalyst is larger than 7.5 nm and smaller than 9.5 nm.

The hydrogenation treatment catalyst may contain an inorganic oxide carrier and an active ingredient supported on the inorganic oxide carrier. At this time, the active ingredient contains phosphorus, an iron group element and a group 6 element.

As the inorganic oxide carrier, a fire-resistant inorganic oxide carrier is preferable, and for example, alumina, silica, titania, magnesia, zirconia, boron oxide, zinc oxide, zeolite (for example, Y zeolite, ZSM-5 zeolite, etc.), And a mixture thereof and the like.

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

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

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

The phosphorus content in the hydrogenation catalyst may be, for example, 0.1% by mass or more, preferably 1.0% by mass or more. The phosphorus content may be, for example, 4.0% by mass or less, preferably 3.0% by mass or less.

The content of the iron group element in the hydrogenation treatment catalyst may be, for example, 1.0% by mass or more, and preferably 1.5% by mass or more. Further, the content of the iron group element may be, for example, 3.5% by mass or less, and preferably 3.0% by mass or less.

The content of the Group 6 element in the hydrogenation catalyst may be, for example, 5.0% by mass or more, and preferably 6.0% by mass or more. 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, the content of phosphorus, iron group element and group 6 element shows the value measured by ICP emission spectroscopy.

In the hydrogenation 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 hydrogenation treatment catalyst tends to further improve the denitrification activity. The ratio C ₂ / C ₁ is preferably 0.20 or more, and more preferably 0.25 or more. A hydrogenation catalyst having such a ratio of C ₂ / C ₁ tends to further improve the desulfurization activity.

In the hydrogenation catalyst, the ratio C ₁ / C ₃ (molar ratio) of the phosphorus content C _{1 to} the Group 6 element content C ₃ is preferably more than 0.23 and more than 0.40. Is more preferable, and more than 0.50 is further preferable. Such a hydrogenation treatment catalyst tends to further improve the denitrification activity. Also, the ratio C ₁ / C ₃ is preferably less than 1.5, more preferably less than 1.0. Such a hydrogenation treatment catalyst tends to further improve the metal resistance.

In the hydrogenation treatment 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, preferably 0.44. It is more preferably less than, and even more preferably less than 0.42. In such a hydrogenation treatment catalyst, the ratio of the denitrification activity to the desulfurization activity (denitrification selectivity) becomes higher, and a highly denitrified hydrotreated oil tends to be more easily obtained.

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

The average pore size of the hydrogenation catalyst is less than 9.5 nm, preferably less than 9.2 nm, and more preferably less than 9.0 nm. With such a hydrogenation-treated catalyst, the denitrification selectivity is further improved, and a highly denitrified hydrotreated oil tends to be more easily obtained.

In addition, in this specification, the average pore diameter of a hydrogenation treatment catalyst shows the value measured by the nitrogen adsorption method.

The specific surface area of the hydrogenation catalyst is preferably 150 m ² / g or more, more preferably 200 m ² / g or more, preferably 350 m ² / g or less, and more preferably 320 m ² / g or less. With such a hydrogenation treatment catalyst, there is a tendency that more excellent desulfurization activity can be obtained in addition to sufficient desulfurization performance.

As the hydrogenation treatment catalyst, a new catalyst, a regeneration catalyst, or the like can be used without particular limitation.

<Demetallizing catalyst>
In the method for producing a 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 a heavy metal, the reactor may be filled with a demetallizing catalyst on the upstream side of the hydrogenation treatment catalyst. That is, the reactor may be one in which the demetallizing catalyst is filled in the front stage and the hydrogenation treatment catalyst is filled in the rear stage.

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

A preferred example of the demetallization catalyst is one containing an inorganic oxide carrier and an active ingredient supported on the inorganic oxide carrier. As the inorganic oxide carrier, a fire-resistant inorganic oxide carrier is preferable, and examples thereof include alumina, silica, alumina-silica, boron oxide, zinc oxide, and a mixture thereof. Examples of the active ingredient include Group 6 elements such as molybdenum and tungsten, and iron group elements such as cobalt and nickel. In addition, the inorganic oxide carrier may further contain phosphorus.

In the demetallization catalyst, the average pore diameter measured by the nitrogen adsorption method is preferably 10 nm or more, more preferably 12 nm or more. Such demetallization catalysts tend to provide better demetallization activity. The average pore diameter of the demetallizing catalyst is preferably 25 nm or less, more preferably 23 nm or less. Such demetallization catalysts tend to provide better hydrogenation activity and catalyst strength.

The pore volume of the demetallizing catalyst is preferably 0.6 mL / g or more, more preferably 0.65 mL / g or more, preferably 1.0 mL / g or less, and more preferably 0.9 mL / g or less. .. With such a demetallized catalyst, a sufficient catalyst life and catalyst strength tend to be obtained, and more stable operation tends to be possible.

As the demetallizing catalyst, a new catalyst, a regenerated catalyst, or the like can be used without particular limitation. Further, the filling ratio of the demetallizing catalyst in the reactor can be appropriately changed according to the operating conditions and the raw material oil composition.

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

<Reaction conditions>
In the method for producing a hydrogenated oil according to the present embodiment, hydrogen is produced by circulating the heavy hydrocarbon oil through a reactor filled with a hydrogenation catalyst and performing the hydrogenation treatment of the heavy hydrocarbon oil. Hydrocarbonated oil is obtained.

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

For example, the reaction temperature of the hydrogenation treatment may be 300 ° C. or higher, and may be 350 ° C. or higher. By setting such a reaction temperature, the activity of the hydrogenation treatment catalyst filled in the reactor tends to be exhibited more remarkably. The reaction temperature of the hydrogenation treatment may be, for example, 500 ° C. or lower, or 450 ° C. or lower. By setting such a reaction temperature, the thermal decomposition of the heavy hydrocarbon oil does not proceed too much, the hydrogenation treatment apparatus can be operated smoothly, and the activity deterioration of the hydrogenation treatment catalyst is suppressed. it can.

The hydrogen partial pressure in the hydrogenation treatment may be, for example, 3 MPa or more, and may be 5 MPa or more. With such a hydrogen partial pressure, the hydrogenation reaction proceeds sufficiently, and there is a tendency that a more highly desulfurized and denitrified hydrotreated oil can be obtained. Further, the hydrogen partial pressure in the hydrogenation treatment may be, for example, 25 MPa or less, and may be 20 MPa or less. Such hydrogen partial pressure tends to be economically advantageous because it avoids an increase in equipment construction cost and operating cost.

The hydrogen / oil ratio in the hydrogenation treatment may be, for example, 400 L / L or 500 L / L. With such a hydrogen / oil ratio, the hydrogenation activity of the hydrogenation treatment catalyst tends to be exhibited more remarkably. Further, the hydrogen / oil ratio in the hydrogenation treatment may be, for example, 3000 L / L and may be 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 such a liquid space velocity, excellent economic efficiency can be ensured. The liquid hourly space velocity in the hydrogenation process can be, for example, a 3.0 h ^-1, may be 2.0 h ^-1. With such a liquid space velocity, a more highly desulfurized and denitrified hydrotreated oil tends to be obtained.

<Hydrogenated oil>
The hydrogenated oil obtained by the method for producing a hydrogenated oil according to the present embodiment is highly desulfurized and denitrified, and can be suitably used as a raw material oil for FCC.

The sulfur content 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. The content of the basic nitrogen content is preferably 0.05% by mass or less, and more preferably 0.04% by mass or less.

The contents of nickel and vanadium in the hydrotreated oil are preferably 10 ppm or less, and more preferably 5 ppm or less. With such a hydrogenated oil, metal poisoning of the catalyst used in the FCC process can be sufficiently suppressed.

According to the production method according to the present embodiment, a hydrotreated oil suitable for the FCC process can be stably produced by an efficient and economical method.

<FCC process>
In the present embodiment, by using the hydrotreated oil obtained by the above-mentioned production method as a raw material oil for FCC, a catalytic cracking oil can be efficiently obtained. That is, the method for producing a catalytic cracking oil according to the present embodiment includes a step of obtaining a hydrocracked oil by the above-mentioned method and a step of obtaining a catalytic cracking oil by fluid cracking of the hydrocracked oil. You can.

In the method for producing catalytic cracking oil according to the present embodiment, the hydrotreated oil obtained by the above-mentioned production method is suitably denitrified as a raw material oil for FCC, so that catalyst deterioration in fluid cracking is sufficient. It is possible to efficiently obtain catalytic cracking oil.

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

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

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

Next, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

<Preparation of raw material oil>
In the following Examples and Comparative Examples, a mixture of atmospheric residual oil A having the following composition and solvent-removing oil in equal volumes was used as the raw material oil.

(Atmospheric pressure residual oil A)
Sulfur content in atmospheric residual oil: 2.9% by mass
Vanadium content in atmospheric residual oil: 40 ppm by mass
Nickel content in atmospheric residual oil: 15 ppm by mass
Content of asphaltene in atmospheric pressure residual oil: 3.0% by mass
Density of atmospheric residual oil at 15 ° C: 0.9619 g / cm ³
Kinematic viscosity of atmospheric residual oil at 100 ° C: 30.5 mm ² / s
Content of residual carbon content (carbon reserve) in atmospheric pressure residual oil: 9.0% by mass
Nitrogen content in atmospheric residual oil: 0.154% by mass
Content of basic nitrogen in atmospheric residual oil: 0.052% by mass

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

<Example 1>
In Example 1, as the demetallizing catalyst, a catalyst (demetallizing catalyst X) in which molybdenum is supported on an alumina carrier in an amount of 2.7% by mass (molybdenum element equivalent) (average pore diameter: 18 nm, pore volume: 0.87 mL / g) was used. Further, as the hydrogenation treatment catalyst, the catalyst A having the composition shown in Table 1 was used. 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 The ratio of the phosphorus content C ₁ to C ₃ is shown, and C ₂ / C ₁ shows the ratio of the iron group element content C _{2 to} the phosphorus content C ₁ .

The demetallizing catalyst X was filled on the reactor inlet side of the hydrogenation treatment apparatus, and the catalyst A having the same capacity was filled on the subsequent stage side. Using this hydrogenation treatment apparatus, hydrogenation treatment was carried out under the following conditions.
Hydrogen partial pressure: 14.4Mpa
Hydrogen / oil ratio: 1000L / L
LHSV: 0.44h ^-1

The reaction temperature was changed to 360 ° C, 380 ° C and 400 ° C, and the sulfur content, nitrogen content and heavy metals of the hydrotreated oil obtained under each condition were analyzed, and the desulfurization activity (kHDS) was determined based on the analysis results. , Denitrogen activity (kHDN), and demetallization activity (kHDM) were determined. The reaction rate constants at each reaction temperature were calculated assuming that each activity had a reaction order, a desulfurization reaction was a secondary reaction, a denitrification reaction was a primary reaction, and a metal removal reaction was a primary reaction, and the relative ratio to Comparative Example 4 described later was calculated. It was calculated as the average value of.

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 hydrogenated oil at the reaction temperature of 380 ° C. The ratio of denitrification activity to desulfurization activity (kHDN / kHDS) was defined as HDN selectivity. Further, as an index of the catalyst life of the hydrogenation treatment catalyst, the time until the activity decreases to 20% with respect to the initial desulfurization activity is measured, and the relative value with respect to Comparative Example 4 described later is obtained, and this is used as the relative metal resistance. And said.

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

<Examples 2 to 4>
The hydrogenation treatment and the obtained hydrogenation treatment 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 hydrogenation treatment catalyst. .. The analysis results are shown in Table 2.

<Comparative Examples 1 to 4>
The hydrogenation treatment and the obtained hydrogenation treatment 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 hydrogenation treatment catalyst. .. The analysis results are shown in Table 2.

Comparing the examples and the comparative examples, high denitrification selectivity and basic nitrogen removal rate were obtained in the examples while suppressing a significant decrease in catalyst life (relative metal resistance).

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

First, the demetallizing catalyst X and the demetallizing catalyst Y (average pore diameter 18 nm, pore volume: equivalent) carrying 6% by mass of molybdenum (equivalent to molybdenum element) and 1.5% by mass of nickel (equivalent to nickel element) on an alumina carrier: 0.80 mL / g), the desulfurization catalyst E, the desulfurization catalyst H, and the desulfurization catalyst A were prepared. Further, as a raw material oil for hydrogenation treatment, a mixture of the solvent-removing oil and the atmospheric residual oil B shown below at a ratio of 54:46 (volume ratio) was prepared.

(Atmospheric pressure residual oil B)
Sulfur content in atmospheric residual oil: 0.92% by mass
Vanadium content in atmospheric residual oil: 11 parts by mass ppm
Nickel content in atmospheric residual oil: 11% by mass ppm
Content of asphaltene in atmospheric pressure residual oil: 0.2% by mass
Density of atmospheric residual oil at 15 ° C: 0.9187 g / cm ³
Kinematic viscosity of atmospheric residual oil at 100 ° C: 25.2 mm ² / s
Content of residual carbon content (carbon reserve) in atmospheric pressure residual oil: 5.1% by mass
Nitrogen content in atmospheric residual oil: 0.170% by mass
Content of basic nitrogen in atmospheric residual oil: 0.057% by mass

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

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

In the MAT test, FCC raw material oil A, which was a mixture of the reduced pressure light oil shown in Table 3 and the desulfurized oil 5A at a ratio of 57:43 (mass ratio), was used as the raw material oil. The MAT test was conducted 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 demetallizing catalyst X and the demetallizing 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 from the inlet side in this order, and the amount of the catalyst used is adjusted. The hydrogenation treatment was carried out in the same manner as in Example 5 except that X: Y: E: H = 22: 22: 23: 33 (volume ratio).

Thirty days after the start of the reaction, the reaction temperature was adjusted so that the sulfur content of the bottom component of the produced oil (residue in distillation separation, fraction having a boiling point of 390 ° C. or higher) was 0.6% by mass, and the average reaction temperature was adjusted. Was 377 ° C. Fractions having a boiling point of less than 390 ° C. of the produced oil were 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 raw material oil B, which was a mixture of the reduced pressure gas oil shown in Table 3 and the desulfurized oil 5B at a ratio of 57:43 (mass ratio), was used as the raw material oil. The MAT test was carried out in the same manner as in Example 5 except that FCC raw material oil B was used as the raw material oil. The test results are shown in Table 4.

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

In Table 3, "density (15 ° C.)" indicates the density at 15 ° C., "LCO fraction" indicates the content of the fraction having a boiling point of 221 ° C. or higher and lower than 343 ° C., and "VR fraction" indicates the boiling point. It shows the content of fractions above 538 ° C. In addition, "residual carbon content", "nitrogen content", "basic nitrogen", "sulfur content", "Ni" and "V" are residual carbon content, nitrogen content, basic nitrogen, sulfur content, nickel and, respectively. Shows the vanadium content. Further, the "average molecular weight" represents the average value of the number of molecular weights of hydrocarbons measured by the GPC apparatus.

In Table 4, "dry gas", "LPG", "WCCG", "LCO", "CLO" and "COKE" are hydrocarbons having 1 or 2 carbon atoms and hydrocarbons having 3 or 4 carbon atoms, respectively. , A hydrocarbon having 5 or more carbon atoms and a boiling point of less than 221 ° C., a hydrocarbon having a boiling point of 221 ° C. or higher and lower than 343 ° C., a liquid hydrocarbon having a boiling point of 343 ° C. or higher, and a solid product. In addition, "decomposition rate" indicates the ratio of the amount obtained by excluding LCO, CLO and coke from all products.

As shown in Table 3, in the hydrogenation treatment of Example 5, although 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.), basic nitrogen. The amount of is reduced as compared with Comparative Example 5. Further, as shown in Table 4, in the catalytic cracking reaction of Example 5, the amount of coke produced was suppressed as compared with Comparative Example 5. Further, as shown in Table 4, in Example 6 in which the catalyst / raw material oil ratio was adjusted so that the amount of coke produced was about the same as in Comparative Example 5, a higher decomposition rate was obtained as compared with Comparative Example 5.

Claims (6)

Atmospheric residue, vacuum distillation residual oil, and the heavy hydrocarbon oil containing at least one selected from the group consisting of raw material to solvent deasphalted oil and visbreaking oil them, hydrotreating catalyst packed It is equipped with a process to obtain hydrocarbonated oil by distributing it to the prepared reactor.
The hydrogenation catalyst contains phosphorus, a group 6 element, and a group 6 element.
In the hydrogenation catalyst,
The ratio C ₂ / C ₁ of the iron group element content C _{2 to} the phosphorus content C ₁ is less than 0.60 in terms of molar ratio.
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 terms of molar ratio.
The ratio C ₁ / C ₃ of the phosphorus content C _{1 to} the content C ₃ of the Group 6 element is 0.78 or more in terms of molar ratio.
The average pore size of the hydrogenation catalyst is larger than 7.5 nm and smaller than 9.5 nm.
Method for producing hydrotreated oil. The production method according to claim 1, wherein the ratio C ₁ / C ₃ is less than 1.5 in terms of molar ratio. The production method according to claim 1 or 2, wherein the ratio C ₂ / C ₁ is 0.20 or more in terms of molar ratio. The production method according to any one of claims 1 to 3, wherein the ratio C ₂ / C ₁ is less than 0.53 in terms of molar ratio. It is provided with a step of distributing heavy hydrocarbon oil to a reactor filled with a hydrogenation treatment catalyst to obtain hydrogenation treatment oil.
The content of heavy metals in the heavy hydrocarbon oil, more than 3 mass ppm, Ri der than 200 mass ppm,
The hydrogenation treatment catalyst contains phosphorus, an iron group element, and a group 6 element.
In the hydrogenation catalyst,
The ratio C ₂ / C ₁ of the iron group element content C _{2 to} the phosphorus content C ₁ is less than 0.60 in terms of molar ratio.
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 terms of molar ratio.
The ratio C ₁ / C ₃ of the phosphorus content C _{1 to} the content C ₃ of the Group 6 element is 0.78 or more in terms of molar ratio.
The average pore size of the hydrogenation catalyst is larger than 7.5 nm and smaller than 9.5 nm.
Method for producing hydrotreated oil . A step of obtaining a hydrotreated oil by the production method according to any one of claims 1 to 5 .
The step of obtaining catalytically cracked oil by fluid cracking of the hydrotreated oil, and
A method for producing a cracked oil.