JP3001775B2 - Crude oil hydrorefining method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for hydrorefining crude oil. More specifically, in the batch hydrodesulfurization process of crude oil excluding crude oil or naphtha fraction, high-quality kerosene and
The present invention relates to a crude oil hydrorefining method capable of increasing the production of light oil and simplifying the refinery equipment.

[0002]

2. Description of the Related Art Conventionally, as a method for refining crude oil, generally, a method has been adopted in which crude oil is distilled under normal pressure to separate each fraction, and then each of the separated fractions is desulfurized. However, this method has a problem that the number of essential oil facilities is large, the process is complicated, and the cooling and heating of the product are repeated, resulting in poor energy efficiency. There is a need for a crude oil treatment method. From such a viewpoint, in recent years, a batch treatment of crude oil excluding a naphtha fraction has been attempted. For example,
(1) A method in which a naphtha fraction in crude oil is separated by distillation, and then the residual oil excluding the naphtha fraction is subjected to lump hydrodesulfurization treatment, followed by distillation and separation into respective products (Japanese Patent Laid-Open No. 3-294390). , (2) After the naphtha fraction in the crude oil is separated by distillation, the residual oil excluding the naphtha fraction is subjected to lump hydrodesulfurization treatment,
Then, the light fraction and the heavy fraction are separated in a high-pressure separation tank,
Method for hydrorefining the obtained light fraction (Japanese Patent Laid-Open No. 4-2)
No. 24890), (3) After the naphtha fraction in crude oil is separated by distillation, the residual oil excluding the naphtha fraction is subjected to lump hydrodesulfurization treatment, and then the light fraction and the heavy fraction are separated in a high-pressure separation tank. And the obtained heavy fraction is subjected to catalytic cracking at a temperature of about 500 ° C. in a nitrogen atmosphere at almost atmospheric pressure, and gasoline and LC
After obtaining O, a method of hydrorefining the light fraction separated from the LCO under high pressure (JP-A-4-224892),
(4) A method of adjusting the product yield by carrying out residual oil fluid catalytic cracking or residual oil hydrocracking after performing crude oil batch processing and atmospheric distillation (US Pat. No. 3,617,501) is proposed. Have been. However, in the above method (1), since a usual desulfurization catalyst is used, a kerosene / light oil fraction of stable quality cannot be obtained, and the effect of increasing white oil production is not satisfactory. In the above method (2), the properties of kerosene oil can be enhanced, but the yield cannot be adjusted sufficiently, and there is a limit to the crude oil that can be used depending on the demand structure. Further, in the method (3), while increasing gasoline production, LCO corresponding to the boiling point range of kerosene light oil is also produced. This LCO has a very high aromaticity, and the smoke point and the smoke point of the kerosene fraction are increased. The cetane number of the gas oil fraction is extremely low. In order to hydrogenate such LCO and obtain a sufficient smoke point or cetane number, a severe and high-temperature and high-pressure device is required. Further, since it is necessary to repressurize the LCO to the reaction pressure, fixed cost, Satisfactory economic efficiency has not been obtained for both variable costs. In the method (4), the quality of the middle distillate obtained by fluid catalytic cracking, such as the hue of light kerosene, the smoke point of kerosene, and the cetane index of light oil, is very poor. On the other hand, in hydrocracking, the temperature and pressure once reduced by atmospheric distillation are reduced to 3
00-450 ° C, high temperature of 100-200kg / cm ²
Since the pressure must be increased, the process is not always satisfactory in terms of energy efficiency and economy. As described above, the conventional method for the active treatment of crude oil excluding the naphtha fraction is difficult to obtain a kerosene / light oil fraction with stable quality, and the facility and operation costs are high. From
The fact is that it has not yet been put to practical use.

[0003]

SUMMARY OF THE INVENTION Under such circumstances, the present invention provides a process for producing a highly saturable middle distillate by hydrocracking of a residual oil in a batch hydrodesulfurization step of a crude oil excluding a crude oil or a naphtha fraction. It is an object of the present invention to provide an economically advantageous crude oil hydrorefining method capable of increasing the production of kerosene / light oil of good and stable quality and simplifying refinery equipment. .

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, hydrodesulfurized crude oil or crude oil excluding a naphtha fraction in the presence of a catalyst, In the hydrorefining method of distilling and separating each product, after separating gas components and liquid hydrocarbon components in a high-pressure gas-liquid separation tank following batch hydrodesulfurization, the liquid hydrocarbon is brought into contact with a catalyst. It has been found that by performing the hydrocracking in this manner, a highly saturable middle distillate is produced, and the quality as well as the yield of the middle distillate can be improved. The present invention has been completed based on such findings.

That is, the present invention relates to (1) hydrodesulfurization of a crude oil or a crude oil excluding a naphtha fraction by contact with a catalyst in the presence of hydrogen and subjecting the effluent to a gas component 1 in a high-pressure gas-liquid separation tank.
And the liquid hydrocarbon component 1 and the liquid hydrocarbon component 1
Is subjected to hydrocracking by contacting with a catalyst in the presence of hydrogen, and then the gaseous component 1 and the effluent from the hydrocracking are combined and subjected to atmospheric distillation to obtain hydrocarbons having different boiling points. (2) Hydrodesulfurization of crude oil excluding crude oil or naphtha fraction;
/ Pressure cm ² under a temperature of 300 to 450 ° C., LHS
V is 0.1 to 3.0 h ^-1 , hydrogen / oil ratio is 300 to 2000 N
hydrorefining method as described in (1) above, which comprises carrying out under the condition of m ³ / kl, (3) catalyst used for hydrodesulfurization is, alumina, silica - selected from boron and phosphorus on an alumina or alumina As a carrier to which at least one compound is added,
The hydrotreating method according to the above (1), wherein (4) the hydrocracking is carried out by using at least one metal selected from metals belonging to Group 8, 9, or 10.
Under a pressure of 0 to 200 kg / cm ² , at a temperature of 300 to 450 ° C., an LHSV of 0.1 to 3.0 h ⁻¹ and a hydrogen / oil ratio of 30
The hydrorefining method according to the above (1), wherein the catalyst used for the hydrocracking is crystalline aluminosilicate or an inorganic oxide comprising the crystalline aluminosilicate or 0 to 2000 Nm ³ / kl. Wherein the carrier comprises at least one selected from metals belonging to Groups 6, 8, 9 or 10 of the periodic table on a carrier comprising a mixture of (6) The gaseous component to be subjected to atmospheric distillation together with the effluent from the hydrocracking further removes the gaseous component 1 decomposed in the high-pressure gas-liquid separation tank by 3
Under a pressure of 0 to 200 kg / cm ² , at a temperature of 300 to 450 ° C., an LHSV of 0.5 to 8.0 h ⁻¹ and a hydrogen / oil ratio of 20
The hydrorefining method according to the above (1), which is obtained by contacting with a hydrorefining catalyst under the conditions of 0 to 2000 Nm ³ / kl, and (7) a hydrorefining catalyst, Alumina, silica, silica-alumina or alumina to which at least one compound selected from boron and phosphorus is added as a carrier is used.
The hydrorefining method according to the above (6), wherein the effluent from the hydrocracking is carried out, wherein the effluent from the hydrocracking is at least one selected from metals belonging to Group 8, 9, or 10. The gas component 2 and the liquid hydrocarbon component 2 are separated in a high-pressure gas-liquid separation tank, and the gas component 2 and the gas component 1 are combined together under a pressure of 30 to ²⁰⁰ kg / cm ² under a pressure of 300 to 200 kg / cm ^2.
At a temperature of 450 ° C., LHSV is 0.5-8.0 h ⁻¹ , hydrogen /
(1) The above-mentioned (1), wherein the oil which has been brought into contact with the hydrorefining catalyst under the condition of an oil ratio of 200 to 2000 Nm ³ / kl is subjected to atmospheric distillation together with the liquid hydrocarbon component 2. A hydrorefining method.

Hereinafter, the present invention will be described in more detail. As a method of separating each petroleum product, usually, crude oil is first supplied to a pre-distillation column to remove a naphtha fraction, then the residual oil is hydrodesulfurized, and then guided to an atmospheric distillation column, and the naphtha fraction is removed. , A method for separating kerosene fraction, gas oil fraction and residual oil, or after direct hydrodesulfurization of crude oil, it is led to atmospheric distillation column and separated into naphtha fraction, kerosene fraction, gas oil fraction and residual oil There is a way. That is, in the present invention, the crude oil from which the naphtha fraction has been removed in the pre-distillation tower may be subjected to batch hydrogenation treatment,
When it is not necessary to make the sulfur content of the naphtha fraction less than about 1 ppm, for example, when the naphtha fraction is used as a raw material for an ethylene production device, the crude oil is removed without removing the naphtha fraction in a pre-distillation column. Hydrotreatment may be performed directly and collectively.

As the crude oil to be supplied to the pre-distillation column or the crude oil to be supplied to the hydrotreating step, generally available crude oil or crude oil from which a naphtha fraction has been removed can be used. In order to prevent contamination and clogging of the inside, prevent deterioration of the hydrotreating catalyst, and the like, desalination treatment is preferably performed in advance. As the desalting method, a method generally used by those skilled in the art can be used, and examples thereof include a chemical desalting method, Petreco's electric desalination method, and Howe-Baker's electric desalination method. .

When the crude oil is treated in the pre-distillation column as described above, the naphtha fraction and the lighter fraction in the crude oil are removed.
The temperature ranges from 145 to 200 ° C. and the pressure ranges from normal pressure to 10 kg / cm ² , preferably 1.5 kg / cm 2
It is around ² . The naphtha fraction removed from the top of this preliminary distillation column has a boiling point of 10 ° C. or higher and an upper limit of 125 to 17
It is preferably in the range of 4 ° C., but since it is hydrodesulfurized and rectified in the subsequent stage, it is not necessary to perform distillation with high precision. The naphtha fraction having a boiling point of 10 to 125 ° C. usually has 5 to 8 carbon atoms, and the naphtha fraction having a boiling point of 10 to 174 ° C. generally has 5 to 10 carbon atoms. If the naphtha fraction is cut at a boiling point of less than 125 ° C., the hydrogen partial pressure may decrease during the next step of hydrotreating, and the efficiency of the hydrotreating may decrease. When cut, the smoke point of the kerosene fraction obtained in the subsequent hydrotreating and distillation tends to decrease.

The crude oil used in the present invention or the crude oil from which the naphtha component has been removed by the above-mentioned pre-distillation method, contains a metal component composed of at least one of vanadium, nickel and iron in an amount of 135 ppm by weight or less and an asphaltene component in an amount of 12% by weight or less. Those containing are preferably used. If the metal component exceeds 135 ppm by weight,
It is not preferable because the catalyst life is remarkably shortened due to the accumulation of metal components, and those having an asphaltene content exceeding 12% by weight are not preferable because the catalyst life is remarkably shortened due to carbon deposition.

[0010] The hydrorefining method of the present invention comprises the step of:
In the presence of hydrogen, it is brought into contact with a catalyst for hydrodesulfurization, and the effluent is separated into a gas component 1 and a liquid hydrocarbon component 1 in a high-pressure gas-liquid separation tank, and the liquid hydrocarbon component 1 is separated from the catalyst in the presence of hydrogen. And then subjecting the gaseous component 1 and the effluent from the hydrocracking to distillation under normal pressure to obtain hydrocarbons having different boiling points.

The hydrodesulfurization used in the above hydrodesulfurization step
In the sulfurizing equipment, crude oil or naphtha fraction is excluded.
The following conditions are used as reaction conditions when hydrorefining oil.
Used. First, the reaction temperature ranges from 300 to 450 ° C.
Is preferred. When the reaction temperature is lower than 300 ° C,
The reaction progress is extremely slow.
Solid carbon (coke) is generated on the medium, significantly increasing the catalyst life
Lower. For the same reason as above, the reaction temperature is 360
The range of -420 ° C is more preferred. Also, the reaction pressure,
The hydrogen partial pressure is 30-200kg / cm^TwoPreferred range
No. The above pressure is 30kg / cm^TwoLess than solid
Precipitates carbon, significantly reduces catalyst life, and
g / cm^TwoPressures above are uneconomical in equipment design. Up
For the same reason as described above, the hydrogen partial pressure is 100 to 180 kg /
cm^TwoMore preferably, it is within the range. In addition, hydrogen /
Oil ratio is 300-2000Nm^Three/ Kiloliter range
Preferably, there is. The above ratio is 300Nm^Three/ Kirori
If the amount is less than 2 liters, hydrorefining does not proceed sufficiently,
000Nm^ThreeIf it exceeds / kiloliter, the equipment design
It is uneconomical. For the same reason as above, the ratio is 5
00-1000Nm ^Three/ Kiloliter range
Is more preferred. The liquid hourly space velocity (LHSV) is 0.1 to 3.
0h^-1Is preferable. LHSV is 0.1h^-1Less than
In this case, an economically sufficient processing speed cannot be obtained, and 3.0 h
^-1If the reaction time exceeds
There is a disadvantage that the purification is not completed. Same reason as above
LHSV is 0.2-0.8h^-1Range
Preferred.

As the catalyst used in the hydrodesulfurization step, alumina, silica-alumina or alumina obtained by adding at least one compound selected from boron and phosphorus to alumina is used as a carrier. , 9
Alternatively, a catalyst supporting at least one selected from metals belonging to group 10 is preferably used. As the metal belonging to group 6 of the periodic table, tungsten and molybdenum are preferable, and groups 8 to 10 of the periodic table are preferably used. Nickel and cobalt are preferable as the metal belonging to. Note that the Group 6 metal and the Group 8 to 10 metals may be used alone or in combination of a plurality of types of metals. In particular, the hydrogenation activity is high and the deterioration is small. ,
Ni-Mo, Co-Mo, Ni-W, Ni-Co-Mo
And the like are preferred.

The amount of the metal carried is not particularly limited, and may be appropriately selected according to various conditions.
Usually 1 to 35 as metal oxide based on the total weight of the catalyst
% By weight. If the supported amount is less than 1% by weight,
If the effect of the hydrotreating catalyst is not sufficiently exhibited, and if it exceeds 35% by weight, the improvement of the hydrogenation activity is not remarkable for the supported amount, and it is economically disadvantageous. In particular,
The range of 5 to 30% by weight is preferred from the viewpoint of hydrogenation activity and economy.

In the case where the catalyst is obtained by adding at least one compound selected from boron and phosphorus to alumina, the catalyst may be a boron compound, a silicon compound or a phosphorus compound based on the total weight of the carrier. Those containing at a ratio of 0.5 to 20% by weight are preferred. When the content is less than the lower limit, the effect of improving the hydrogenation activity is small, and when the content exceeds the upper limit, the effect of improving the hydrogenation activity is not so much seen for the amount,
It is not economical and the desulfurization activity may decrease, which is not preferable. In particular, each is preferably in the range of 1 to 18% by weight from the viewpoint of improving the hydrogenation activity.

The carrier is prepared by adding a boron compound or a phosphorus compound at a predetermined ratio to alumina or an alumina precursor having a water content of 65% by weight or more,
At a temperature of about 1 hour or more, more preferably
After heating and kneading for 1.5 hours or more, it can be produced by molding, drying and sintering by a known method. If the heating and kneading is less than 1 hour, kneading may be insufficient and the dispersion state of boron atoms and the like may be insufficient, and if the kneading temperature is out of the above range, boron and the like may not be highly dispersed, Not preferred. The addition of boron, silicon, phosphorus or a compound thereof may be carried out in a solution by heating and dissolving in water, if necessary.

The alumina precursor is not particularly limited as long as it produces alumina by firing. Examples of the alumina precursor include alumina hydrates such as aluminum hydroxide, pseudoboehmite, boehmite, bayerite, and gibbsite. Can be mentioned. The above-mentioned alumina or alumina precursor is desirably used with a water content of 65% by weight or more. If the water content is less than 65% by weight, the added compounds such as phosphorus may not be sufficiently dispersed. .

As the boron compound, besides boron oxide, various boron compounds which can be converted into boron oxide by calcination can be used. For example, boric acid, ammonium borate, sodium borate, perborate Examples include sodium silicate, orthoboric acid, tetraboric acid, boron pentasulfide, boron trichloride, ammonium perborate, calcium borate, diborane, magnesium borate, methyl borate, butyl borate, and tricyclohexyl borate. The phosphorus compound used in the carrier obtained by adding a phosphorus compound to alumina among the above carriers may include simple phosphorus. Specific examples of the phosphorus simple substance include yellow phosphorus and red phosphorus.

Examples of the phosphorus compound include inorganic phosphoric acids having a low oxidation number such as orthophosphoric acid, hypophosphoric acid, phosphorous acid, and hypophosphorous acid, or alkali metal salts or ammonium salts thereof, pyrophosphoric acid, tripolyphosphoric acid, tetraphosphoric acid, and the like. Polyphosphoric acid such as polyphosphoric acid or alkali metal salt or ammonium salt thereof, metaphosphoric acid such as trimetaphosphoric acid, tetrametaphosphoric acid, hexametaphosphoric acid or alkali metal salt or ammonium salt thereof, phosphorus chalcogenide, organic phosphoric acid, organic phosphoric acid And the like. Among these, an alkali metal salt or an ammonium salt of inorganic phosphoric acid or condensed phosphoric acid having a low oxidation number is particularly preferable from the viewpoints of activity, water resistance, heat resistance and durability.

As the silica-alumina, for example, a molar ratio of silica to alumina of SiO ₂ / Al ₂ O ₃ is 3.5.
The faujasite-type zeolites described above are exemplified. Among them, the molar ratio of SiO ₂ / Al ₂ O ₃ is 4.
Six or more are preferable from the viewpoint of heat resistance.

The average pore diameter of the above catalyst is 80 to 120.
Å is preferable, and the average pore diameter is 80
If it is less than Å, heavy molecules cannot be sufficiently diffused into the pores, the reaction becomes insufficient, and the properties of the residual oil (for example, Ni, V
Is not preferred. On the other hand, if it exceeds 120 °, the surface area becomes small and the reaction does not proceed sufficiently. In the present invention, the catalyst layer made of the catalyst having the above composition is further divided into two stages,
Catalyst having an average pore diameter in the range of from about 1000 to about 5000, preferably from about 1000 to about 3000,
It is more preferable to use a combination of catalysts having a mean average pore diameter in view of the catalyst life.

In the present invention, the above-mentioned hydrodesulfurized crude oil is gas-liquid separated into a gas component 1 and a liquid hydrocarbon component 1, and then the liquid hydrocarbon component 1 is hydrocracked. Such gas-liquid separation can be carried out preferably by using a high-pressure gas-liquid separation tank because the separation can be performed without largely changing the temperature and pressure of the effluent. In the hydrocracking apparatus used in the hydrocracking treatment, the following conditions are used as the reaction conditions. First, the reaction temperature is 300 to 450
C. is preferred. When the reaction temperature is lower than 300 ° C., the progress of the reaction is remarkably slowed. When the reaction temperature is higher than 450 ° C., over-decomposition proceeds, and the yield of the intermediate product decreases due to an increase in gas yield, which is uneconomical. . For the same reason as above, the reaction temperature is more preferably in the range of 360 to 420 ° C. The reaction pressure, that is, the hydrogen partial pressure is 30 to 200.
The range of kg / cm ² is preferred. The above pressure is 30kg /
If it is less than ² cm ² , the properties of the generated middle distillate, for example, hue, smoke point, etc., will deteriorate, and a pressure exceeding 200 kg / cm ² will be uneconomical in terms of equipment design. For the same reason as above, the hydrogen partial pressure is more preferably in the range of 100 to 180 kg / cm ² . Furthermore, the hydrogen / oil ratio is between 300 and 2
It is preferably in the range of 000 Nm ³ / kl. When the above ratio is less than 300 Nm ³ / kl, the reaction does not proceed sufficiently and the product properties of the cracked oil deteriorate, and when it exceeds 2000 Nm ³ / kl, it is uneconomical in terms of equipment design. For the same reasons as above,
More preferably, the ratio is in the range of 500-1000 Nm ³ / kl. LHSV is 0.1-3.0h
It is preferably in the range of ^-1 . When the LHSV is less than 0.1 h ^-1 , a sufficient processing speed cannot be obtained from an economic viewpoint, and when the LHSV exceeds 3.0 h ^-1 , the reaction time is insufficient and the yield of cracked oil is sufficiently obtained. I can't. For the same reason as above, the LHSV is more preferably in the range of 0.2 to 0.8 h ^-1 .

As the catalyst used in the hydrocracking treatment, for example, the catalyst disclosed in Japanese Patent Publication No.
A generally known zeolite-based residue cracking catalyst described in column 18, line 18 to column 6, line 30 can be used. A crystalline aluminosilicate, preferably an iron-containing aluminosilicate, or a mixture thereof with an inorganic oxide is used as a carrier, and at least one selected from metals belonging to Groups 6, 8, 9, and 10 of the periodic table. Can be used. Particularly, as the carrier, 10 to 90% by weight of iron-containing aluminosilicate and inorganic oxide 9
What consists of 0-10 weight% is preferable. When the content of the iron-containing aluminosilicate in the support is less than 10% by weight, the effect as a hydrotreating catalyst is not sufficiently exhibited,
On the other hand, if it exceeds 90% by weight, the effect of improving the hydrogenation activity is not so much for the amount, and it is economically disadvantageous. In particular, from the viewpoint of hydrogenation activity and economy, 30 to 70% by weight of iron-containing aluminosilicate and 70 to 70% of inorganic oxide
Those comprising 30% by weight are preferred.

Examples of the inorganic oxide used for the iron-containing aluminosilicate-containing carrier include alumina such as boehmite gel and alumina sol, silica such as silica sol, and porous materials such as silica-alumina. It is preferably used.

In the present invention, the catalyst used in the hydrocracking treatment is selected from the metals belonging to Group 6, 8, 9 or 10 of the periodic table on the carrier obtained as described above. At least one type is supported, but the supporting method is not particularly limited, and any known method such as an impregnation method, a coprecipitation method, and a kneading method can be adopted. Further, after a desired metal is supported on the carrier at a predetermined ratio, drying is performed, if necessary, followed by baking treatment. The sintering temperature and time are appropriately selected according to the type of the metal supported, and the like. In addition, Periodic Table 6, 8, 9
Alternatively, as the metal belonging to Group 10, the same metals as described in the hydrodesulfurization treatment can be used. The hydrocracking catalyst thus obtained has an average pore diameter of 10
Those having a thickness of 0 to 200 ° are preferred. This average pore diameter is 10
If it is less than 0 °, the reaction does not proceed sufficiently because the heavy molecules do not sufficiently diffuse into the pores. On the other hand, if it exceeds 200 °, the surface area becomes small and the progress of the reaction is insufficient.

In the present invention, after the hydrodesulfurization,
One gas component obtained by gas-liquid separation in a pressure gas-liquid separation tank
And further hydrorefining treatment can be performed if necessary.
You. In the hydrorefining equipment used in the above hydrotreating process
The following conditions are used as the reaction conditions. Ma
The reaction temperature is preferably in the range of 300 to 450 ° C. Up
When the reaction temperature is lower than 300 ° C., the progress of the reaction is remarkable.
If the temperature exceeds 450 ° C, excessive decomposition proceeds
As the gas yield increases, the yield of intermediate products decreases,
Already. For the same reason as above, the reaction temperature is 3
The range of 60 to 420C is more preferable. Also, the reaction pressure
Force, ie hydrogen partial pressure is 30-200 kg / cm ^TwoAnd one more
00-180kg / cm^TwoIs preferable. Above pressure
Is 30kg / cm^TwoIs sufficient, but high pressure gas-liquid separation
It is economical to supply the gas components in the tank to the reactor as they are
Therefore, the pressure of this process is
Determined by conditions. Furthermore, the hydrogen / oil ratio is between 200 and 2
000Nm^Three/ Kl, and 500-1500N
m^Three/ Kiloliter. the above
The ratio is 200Nm^ThreePer kiloliter is sufficient
Supplies the gas component in the high-pressure gas-liquid separation tank to the reactor as it is
Hydrogen / oil for this process because it is economical to
The ratio is determined by the conditions of the preceding hydrodesulfurization. LHS
V is 0.5-8.0h^-1Is preferably within the range. LH
SV is 0.5h^-1If the value is less than
Speed cannot be obtained, and 8.0h^-1If the reaction exceeds
The interval is insufficient, and the yield of cracked oil cannot be obtained sufficiently. Above and
For the same reason, LHSV is 1.0-5.0h.^-1In the range
More preferably,

As the hydrorefining catalyst used in the above hydrotreating treatment, alumina or silica, a compound obtained by adding a boron and / or phosphorus compound to alumina, or an iron-containing aluminosilicate as a carrier is used. A catalyst supporting at least one selected from metals belonging to Groups 6, 8, 9, or 10 is preferably used. As such a material, those similar to those used in the above hydrodesulfurization or hydrocracking treatment can be used. Such a hydrorefining catalyst preferably has an average pore diameter of 20 to 60 °. If the average pore diameter is less than 20 °, the diffusion resistance in the catalyst will increase and the reaction will not proceed sufficiently. On the other hand, if it exceeds 60 °, the surface area becomes small and a sufficient reaction rate cannot be obtained.

In the present invention, the effluent from the hydrocracking is further separated into a gas component 2 and a liquid hydrocarbon component 2 in a high-pressure gas-liquid separation tank, and the gas component 2 is separated from the high-pressure gas after the hydrodesulfurization. 30 to 2 together with the gas component 1 from the liquid separation tank
Under a pressure of 00 kg / cm ² and a temperature of 300 to 450 ° C., an LHSV of 0.5 to 8.0 h ⁻¹ and a hydrogen / oil ratio of 200 to
A method in which a catalyst which has been brought into contact with a hydrorefining catalyst under the condition of 2000 Nm ³ / kl together with the liquid hydrocarbon component 2 and subjected to atmospheric distillation can be preferably used. By adopting such a method, advantages such as improvement of the smoke point of kerosene, improvement of the hue of light oil, and improvement of the cetane number can be obtained.

When the crude oil is directly subjected to hydrodesulfurization, etc.,
The reaction conditions are basically the same as those for the hydrodesulfurization treatment of crude oil excluding the naphtha fraction. However, since the hydrogen partial pressure decreases, the hydrogen partial pressure and the hydrogen / oil ratio are adjusted as described above. It is preferable to increase the value within the range. In this way,
After the crude oil or the crude oil excluding the naphtha fraction is subjected to a batch hydrodesulfurization treatment, the treated oil is subjected to various products in an atmospheric distillation column, for example, a naphtha fraction, a kerosene fraction, a gas oil fraction, and an atmospheric distillation residue. And so on. At this time, the operating conditions of the atmospheric distillation column are the same as those of the crude oil atmospheric distillation method widely used in petroleum refining equipment, and the normal temperature is about 300 to 380 ° C and the pressure is ordinary pressure to 1.0 kg / It is about cm ² G. By performing this step subsequent to the hydrodesulfurization step, heat recovery can be achieved and operating costs can be greatly reduced. In addition, in order to effectively use the existing crude oil atmospheric distillation column, the construction cost can be reduced by transferring the hydrodesulfurized oil to a refinery located elsewhere and separating the product.

[0029]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Example 1 As a raw material oil, the following properties except for a naphtha fraction (C5 to 157 ° C) of Arabian heavy desalted crude oil were used. Feedstock A density (15 ° C) 0.9319 g / cm ³ Sulfur content 3.24 wt% Nitrogen 1500 wtppm Vanadium 55 wtppm Nickel 18 wtppm Iron 1.5 wtppm Asphaltene content 9.9 wt% Kerosene fraction (Higher than 157 ° C and lower than 239 ° C) 9.8% by weight Gas oil fraction (higher than 239 ° C and lower than 370 ° C) 25.8% by weight Residual oil (higher than 370 ° C) 64.4% by weight As shown in Fig. 1 Then, a feed oil and hydrogen were supplied to a 1000 ml hydrodesulfurization reactor, and a hydrodesulfurization reaction was carried out using the catalyst A shown in Table 1. While maintaining the temperature and pressure after the reaction, high-pressure gas-liquid The mixture was supplied to a separation tank, and the separated liquid component and hydrogen were supplied to a 1000 ml hydrocracking apparatus, and hydrocracking was performed using catalyst D shown in Table 1. Atmospheric distillation was performed by combining the oil produced by the hydrocracking reaction and the above gas components. Table 2 shows the reaction conditions of each reactor. Further, the catalyst A shown in Table 1 was obtained by adding the first catalyst to an alumina carrier.
It is a generally known catalyst prepared by impregnating the water-soluble salts of the components shown in the table. The catalyst D is a generally known catalyst using a mixture of iron-containing Y-type zeolite and alumina as a carrier and impregnating a metal salt from an aqueous solution. The obtained hydrotreated oil was distilled to obtain a naphtha fraction (C5 to 157 ° C or less), a kerosene fraction (above 157 ° C and 239 ° C or less), and a light oil fraction (2
It was fractionated into 39 ° C. or higher and 370 ° C. or lower) and residual oil (higher than 370 ° C.), and the respective properties were determined. Also,
A storage stability test was performed on the kerosene fraction and the gas oil fraction. The results are shown in Tables 3 and 4. In addition, the storage stability test of the kerosene fraction and the gas oil fraction was conducted with a vented 50
400 ml of the sample was placed in a 0 ml glass container and stored in a dark place kept at 43 ° C. for 30 days.
The results before and after the storage test were evaluated and shown. Table 3 and 4
From the table, it is found that kerosene having a good smoke point and gas oil having a good cetane number can be obtained because a middle distillate rich in paraffin is generated by hydrocracking of residual oil.

Example 2 As a raw material oil, a desalted Arabian light crude oil having the following properties was used. Feedstock B density (15 ° C) 0.8639 g / cm ³ Sulfur content 1.93 wt% Nitrogen content 850 wtppm Vanadium 18 wtppm Nickel 5 wtppm Iron 7.0 wtppm Asphaltene content 3.8 wt% Naphtha fraction (C5 to 157 ° C) 14.7% by weight Kerosene fraction (greater than 157 ° C and 239 ° C or less) 14.2% by weight Gas oil fraction (greater than 239 ° C and 370 ° C or less) 25.6% by weight Residue (370 ° C) 45.5% by weight As shown in FIG. 1, a feed oil and hydrogen were supplied to a 1000 ml hydrodesulfurization reactor, and a hydrodesulfurization reaction was carried out using a catalyst C shown in Table 1. While maintaining the temperature and pressure after the reaction, the mixture was supplied to a high-pressure gas-liquid separation tank, and the separated liquid component and hydrogen were supplied to a 1000 ml hydrocracking apparatus. Chemical decomposition was performed. Atmospheric distillation was performed by combining the oil produced by the hydrocracking reaction and the above gas components. Table 2 shows the reaction conditions of each reactor. Further, the catalyst C shown in Table 1 was obtained by adding the first catalyst to the alumina carrier.
It is a generally known catalyst prepared by impregnating the water-soluble salts of the components shown in the table. The catalyst D is a generally known catalyst using a mixture of iron-containing Y-type zeolite and alumina as a carrier and impregnating a metal salt from an aqueous solution. In the same manner as in Example 1,
The obtained hydrotreated oil was distilled, and the properties of each of the obtained fractions were determined. Further, a storage stability test was performed on the kerosene fraction and the gas oil fraction. The results are shown in Tables 3 and 4. It was found that even in the case where Arabian light desalted crude oil was used as a feed oil, the production of a middle distillate having good properties could be increased as in Example 1.

EXAMPLE 3 As shown in FIG. 2, a feed oil B and hydrogen were supplied to a 1000 ml hydrodesulfurization reactor, and a catalyst B shown in Table 1 was used.
A hydrodesulfurization reaction is performed using, and while maintaining the temperature and pressure after the reaction, the mixture is supplied to a high-pressure gas-liquid separation tank, and the separated liquid component and hydrogen are supplied to a 1000 ml hydrocracking apparatus. Hydrocracking was carried out using Catalyst D shown in Table 1. On the other hand, the gaseous component obtained in the high-pressure gas-liquid separation tank was converted into a catalyst E by a 100 ml hydrotreating reactor.
Contact. Atmospheric distillation was performed on the oil produced from the hydrocracking and the gas component from the hydrorefining. Table 2 shows the reaction conditions of each reactor. The catalysts B and E shown in Table 1 are generally known catalysts prepared by impregnating an alumina carrier with a water-soluble salt of the component shown in Table 1. Also,
Catalyst D is a generally known catalyst using a mixture of iron-containing Y-type zeolite and alumina as a carrier and impregnating a metal salt from an aqueous solution. In the same manner as in Example 1, the obtained hydrotreated oil was distilled, and the properties of the obtained fractions were determined. Further, a storage stability test was performed on the kerosene fraction and the gas oil fraction. The results are shown in Tables 3 and 4. By performing the hydrorefining treatment, kerosene oil having even better properties was obtained.

Example 4 As shown in FIG. 3, a feed oil A and hydrogen were supplied to a 1000 ml hydrodesulfurization reactor, and a catalyst B shown in Table 1 was used.
The hydrodesulfurization reaction is carried out using, and the temperature and pressure after the reaction are supplied to the high-pressure gas-liquid separation tank 1, and the separated liquid component 1 and hydrogen are supplied to the 1000 ml hydrocracking reactor. Then, hydrocracking was carried out using Catalyst D shown in Table 1. Further, the effluent after the hydrocracking reaction is maintained in a high-pressure gas-liquid separation tank 2 while maintaining the temperature and pressure.
And gas component 2. On the other hand, the gas components 1 and 2 obtained in the high-pressure gas-liquid separation tanks 1 and 2, respectively,
It was contacted with catalyst F in a 00 milliliter hydrorefining reactor. The liquid component 2 and the gas component obtained by hydrorefining were distilled in the same manner as in Example 1, and the properties of each fraction were evaluated.
Further, a storage stability test was performed on the kerosene fraction and the gas oil fraction. The results are shown in Tables 3 and 4. By further hydrorefining the hydrocracked oil, kerosene oil having better properties in kerosene smoke point and light oil hue was obtained.

Comparative Example 1 As shown in FIG. 4, a feedstock A was subjected to hydrotreating in the same manner as in Example 1 except that only hydrodesulfurization was performed under the conditions shown in Table 2. The properties of each fraction obtained by fractionating the produced oil in the same manner as in Example 1 and the storage stability test for kerosene / light oil components were evaluated in the same manner as in Example 1, and the results were shown in Tables 3 and 4. It is shown in the table. When only hydrodesulfurization is performed in the batch processing of crude oil, it can be seen that the quality is insufficient in all of the amounts of metal and nitrogen in the residual oil, the hue and smoke point of kerosene oil, and the cetane index.

Comparative Example 2 As shown in FIG. 5, feed oil B was directly passed through a hydrocracking apparatus without performing gas-liquid separation at the latter stage of hydrodesulfurization.
The catalysts used and the reaction conditions are shown in Tables 1 and 2.
The properties of each fraction obtained by fractionating the produced oil in the same manner as in Example 1 and the storage stability test for kerosene / light oil components were evaluated in the same manner as in Example 1, and the results were shown in Tables 3 and 4. It is shown in the table. If the light fraction is also supplied to the hydrocracking reactor at the same time without gas-liquid separation, the paraffin content in the kerosene and gas oil will be decomposed more than the heavy matter will be decomposed. In addition, the quality such as light oil cetane number is reduced.

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

[Table 3]

[0038]

[Table 4]

[0039]

According to the present invention, in a batch hydrodesulfurization step of a crude oil excluding a crude oil or a naphtha fraction, a highly saturable middle distillate is obtained by hydrocracking of the residual oil.
Hydro-reforming of light kerosene can be effectively performed in conjunction with hydrodesulfurization of heavy oil, thereby increasing production of high-quality light kerosene and simplifying refining equipment.

[Brief description of the drawings]

FIG. 1 is a schematic process chart showing an example of the hydrorefining method of the present invention used in each of Examples 1 and 2.

FIG. 2 is a schematic process chart showing one example of the hydrorefining method of the present invention used in Example 3.

FIG. 3 is a schematic process chart showing one example of the hydrorefining method of the present invention used in Example 4.

FIG. 4 is a schematic process chart showing an example of the hydrorefining method outside the present invention used in Comparative Example 1.

FIG. 5 is a schematic process chart showing an example of a hydrorefining method outside the present invention used in Example 2.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C10G 65/12 C10G 45/04 C10G 45/12 C10G 47/16

Claims (8)

(57) [Claims] Claims 1. A crude oil or a crude oil excluding a naphtha fraction is subjected to hydrodesulfurization by contact with a catalyst in the presence of hydrogen, and the effluent is converted into a gas component 1 and a liquid hydrocarbon component 1 in a high-pressure gas-liquid separation tank. presence of a separate, hydrogen liquid hydrocarbon components 1, crystalline a
Luminosilicate or its mixture with inorganic oxide
Belonging to group 6, 8, 9 or 10 of the periodic table
Carrying at least one selected from metals
And then hydrocracking by contacting with a catalyst which is a crude oil or a hydrocarbon having a different boiling point by subjecting the gaseous component 1 and the effluent from the hydrocracking to distillation under normal pressure to obtain a hydrocarbon having a different boiling point. A method for hydrorefining crude oil excluding a naphtha fraction. 2. The hydrodesulfurization is performed at 30 to 200 kg / cm.
^At a pressure of ² and a temperature of 300-450 ° C, the LHSV is
^{1 to} 3.0 h ^-1 , hydrogen / oil ratio of 300 to 2000 Nm ³ /
2. The hydrorefining method according to claim 1, wherein the method is carried out under a condition of kiloliters. 3. The catalyst used in hydrodesulfurization is a carrier obtained by adding at least one compound selected from boron and phosphorus to alumina, silica-alumina or alumina as a carrier. 2. The hydrorefining method according to claim 1, wherein at least one selected from metals belonging to Group 10 is supported. 4. The hydrocracking of 30 to 200 kg / cm.
^At a pressure of ² and a temperature of 300-450 ° C, the LHSV is
^{1 to} 3.0 h ^-1 , hydrogen / oil ratio of 300 to 2000 Nm ³ /
2. The hydrorefining method according to claim 1, wherein the method is carried out under a condition of kiloliters. 5. The catalyst used for hydrocracking comprises an iron-containing catalyst.
10 to 90% by weight of aluminosilicate and inorganic oxide 9
2. The hydrorefining method according to claim 1, wherein at least one selected from metals belonging to Group 6, 8, 9 or 10 of the periodic table is carried on a carrier comprising 0 to 10% by weight. Method. 6. The gas component to be subjected to atmospheric distillation together with the effluent from the hydrocracking further comprises a gas component 1 separated in a high-pressure gas-liquid separation tank under a pressure of 30 to ²⁰⁰ kg / cm ² .
At a temperature of 300-450 ° C, LHSV is 0.5-8.0.
h ^-1, hydrorefining method according to claim 1, wherein the hydrogen / oil ratio is obtained by contact with a hydrorefining catalyst under the conditions of 200 to 2000 nm ³ / kl. 7. A hydrorefining catalyst comprising alumina, silica,
A carrier obtained by adding at least one compound selected from boron and phosphorus to silica-alumina or alumina and supporting at least one selected from metals belonging to Groups 6, 8, 9 or 10 of the periodic table The hydrorefining method according to claim 6, wherein 8. An effluent from the hydrocracking is separated into a gas component 2 and a liquid hydrocarbon component 2 in a high-pressure gas-liquid separation tank, and the gas component 2 is combined with the gas component 1 in an amount of 30 to 200 kg.
/ Pressure cm ² under a temperature of 300 to 450 ° C., LHS
V is 0.5 to 8.0 h ^-1 and the hydrogen / oil ratio is 200 to 2000 N
2. The hydrorefining method according to claim 1, wherein the catalyst which has been brought into contact with the hydrorefining catalyst under the condition of m ³ / kl is subjected to atmospheric distillation together with the liquid hydrocarbon component 2.