JPH0841466A - Method for hydrofining crude oil - Google Patents

Abstract

PURPOSE:To increase the production of stabilized kerosene and gas oil high in quality and simplify the refining equipment by collectively hydrodesulfurizing a crude oil or the crude oil removed from a naphtha fraction, then hydrocracking the resultant residual oil and providing an intermediate fraction having high saturation properties. CONSTITUTION:This method for hydrofining a crude oil is to initially bring the crude oil or the one removed from a naphtha fraction into contact with a catalyst in the presence of hydrogen, hydrodesulfurize the crude oil under conditions of preferably 100-180kg/cm<2>, 360-420 deg.C temperature, 500-1000Nm<3>/kl hydrogen/oil ratio and 0.2-0.8hr<-1> liquid hourly space velocity (LHSV), then separate the resultant effluent into a gaseous component and a liquid hydrocarbon component in a high-pressure gas-liquid separating tank, subsequently bring the separated liquid hydrocarbon component into contact with a catalyst in the presence of hydrogen, hydrocrack the liquid hydrocarbon component preferably under the same reactional conditions as those in the hydrodesulfurization, then join the prepared effluent with the gaseous component obtained by the hydrodesulfurization of the crude oil and carry out the atmospheric distillation. Thereby, hydrocarbons different in boiling point are obtained.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Conventionally, as a method for refining crude oil, generally, a method has been employed in which crude oil is subjected to atmospheric distillation to separate each fraction, and then each separated fraction is desulfurized. However, this method is not always satisfactory, because it has a large number of essential oil facilities, complicated processes, and poor energy efficiency due to repeated cooling and heating of the product. Crude oil processing method is required. From such a viewpoint, batch processing of crude oil excluding the naphtha fraction has been attempted in recent years. For example,
(1) A method in which the naphtha fraction in crude oil is separated by distillation, the residual oil from which the naphtha fraction has been removed is subjected to a batch hydrodesulfurization treatment, and then distilled to separate each product (JP-A-3-294390). (2) After distilling and separating the naphtha fraction in the crude oil, the residual oil from which the naphtha fraction has been removed is subjected to a batch hydrodesulfurization treatment,
Then, it is separated into a light fraction and a heavy fraction in a high pressure separation tank,
A method for hydrorefining the obtained light fraction (Japanese Patent Laid-Open No. 4-2 / 1992).
No. 24890), (3) After distilling and separating the naphtha fraction in crude oil, the residual oil excluding the naphtha fraction is subjected to a batch hydrodesulfurization treatment, and then a light fraction and a heavy fraction are separated in a high pressure separation tank. And the resulting heavy fraction was catalytically cracked at a temperature of about 500 ° C. under a nitrogen atmosphere at about atmospheric pressure to give gasoline and LC.
A method of hydrorefining the light fraction separated from this LCO under high pressure after obtaining O (JP-A-4-224892);
(4) Proposal of a method (US Pat. No. 3,617,501) in which a crude oil batch treatment and atmospheric distillation are performed, and then residual oil fluid catalytic cracking or residual oil hydrocracking is performed to adjust the product yield. Has been done. However, in the above method (1), since a normal desulfurization catalyst is used, a kerosene / light oil fraction having stable quality cannot be obtained, and the white oil production increasing effect is not satisfactory. In the method (2), the properties of kerosene can be improved, but the yield cannot be adjusted sufficiently, and the crude oil that can be used is limited depending on the demand structure. Further, in the method of (3), while increasing the production of gasoline, LCO corresponding to the boiling point range of kerosene is also co-produced, but this LCO has a very high aromaticity and the smoke point of the kerosene fraction and The cetane number of the light oil fraction is extremely low. In order to hydrogenate such a LCO and obtain a sufficient smoke point or cetane number, a high-temperature and high-pressure device with high severity is required, and since it is necessary to re-pressurize the LCO to the reaction pressure, fixed costs, Satisfaction with variable costs has not been obtained. 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 the hydrocracking, the temperature and pressure once dropped by the atmospheric distillation are restored to 3
00~450 ℃, high temperature and of 100~200kg / cm ²
Since it has to be a high pressure, it is not always a satisfactory process in terms of energy efficiency and economy. As described above, the conventional active treatment method of crude oil excluding the naphtha fraction is difficult to obtain a kerosene / light oil fraction with stable quality, and the equipment cost and the operating cost are high. From
The reality is that it has not yet been put to practical use.

[0003]

SUMMARY OF THE INVENTION Under the circumstances, the present invention is directed to a high-saturation intermediate fraction by hydrocracking of residual oil in a batch hydrodesulfurization process of crude oil or crude oil excluding naphtha fraction. An object of the present invention is to provide an economically advantageous hydrorefining method for crude oil, which can increase the production of kerosene and light oil of good quality and stable by obtaining the oil, and can simplify the essential oil equipment. .

[0004]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that crude oil or crude oil excluding naphtha fraction is hydrodesulfurized in the presence of a catalyst, and then In the hydrorefining method of distilling and separating each product, after batch hydrodesulfurization, after separating into a gas component and a liquid hydrocarbon component in a high pressure gas-liquid separation tank, the liquid hydrocarbon is contacted with a catalyst. It has been found that, by hydrocracking the resulting mixture, an intermediate fraction having a high degree of saturation can be generated, and the yield and the quality of the intermediate fraction can be improved. The present invention has been completed based on such findings.

That is, according to the present invention, (1) crude oil or crude oil excluding naphtha fraction is brought into contact with a catalyst in the presence of hydrogen to hydrodesulfurize, and the effluent is separated into a gas component 1 in a high pressure gas-liquid separation tank.
And a liquid hydrocarbon component 1 and the liquid hydrocarbon component 1
Is hydrolyzed by contacting with a catalyst in the presence of hydrogen, and then the gas component 1 and the effluent from the hydrocracking are combined and subjected to atmospheric distillation to obtain hydrocarbons having different boiling points. 30 to 200 kg of a method for hydrorefining crude oil or crude oil excluding naphtha fraction, (2) hydrodesulfurization
LHS at a temperature of 300 to 450 ° C. under a pressure of / cm ^2.
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 Using at least one compound added as a carrier,
The method for hydrorefining according to (1) above, which carries at least one selected from metals belonging to Group 8, 9, or 10;
Under a pressure of 0 to 200 kg / cm ² , a temperature of 300 to 450 ° C., an LHSV of 0.1 to 3.0 h ⁻¹ , and a hydrogen / oil ratio of 30.
It is carried out under the conditions of 0 to 2000 Nm ³ / k liter, and (5) the hydrorefining method described in (1) above, and (5) the catalyst used for hydrocracking is crystalline aluminosilicate or an inorganic oxide thereof. The hydrorefining method according to the above (1), characterized in that at least one selected from the metals belonging to Groups 6, 8, 9 or 10 of the Periodic Table is carried on a carrier comprising a mixture of (6) The gas component that is subjected to atmospheric distillation in combination with the effluent from the hydrocracking further decomposes the gas component 1 decomposed in the high-pressure gas-liquid separation tank into 3 parts.
Under a pressure of 0 to 200 kg / cm ² , 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 (1) above, which is obtained by contacting with the hydrorefining catalyst under the condition of 0 to 2000 Nm ³ / kil, and (7) the hydrorefining catalyst, Alumina, silica, silica-alumina, or alumina to which at least one compound selected from boron and phosphorus is added is used as a carrier, and the periodic table
The hydrorefining method according to the above (6), characterized in that it carries at least one selected from the group 8, 9, and 10 metals, and (8) the effluent from the hydrocracking. It 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 under a pressure of 30 to ²⁰⁰ kg / cm ² and 300 to 200 kg / cm ^2.
At a temperature of 450 ° C., LHSV is 0.5 to 8.0 h ⁻¹ , hydrogen /
The above-mentioned (1), characterized in that what is brought into contact with the hydrorefining catalyst under the condition of the oil ratio of 200 to 2000 Nm ³ / kil is combined with the liquid hydrocarbon component 2 and subjected to atmospheric distillation. A hydrorefining method is provided.

The present invention will be described in more detail below. As a method for separating each petroleum product, usually, crude oil is first supplied to a preliminary distillation column to remove the naphtha fraction, and then the residual oil is hydrodesulfurized and then introduced to an atmospheric distillation column to remove the naphtha fraction. , A kerosene fraction, a gas oil fraction and a residual oil, or directly hydrodesulfurizing crude oil and then introducing it to an atmospheric distillation column to separate it into a naphtha fraction, a kerosene fraction, a gas oil fraction and a residual oil. There is a way. That is, in the present invention, crude oil from which the naphtha fraction has been removed may be subjected to batch hydrotreatment in a preliminary distillation column, and
When it is not necessary to reduce the sulfur content of the naphtha fraction to less than about 1 ppm, for example, when the naphtha fraction is used as a raw material for an ethylene production apparatus, crude oil is removed without removing the naphtha fraction in a preliminary distillation column. The hydrogenation may be carried out directly and collectively.

As the crude oil to be supplied to the preliminary distillation column or the crude oil to be supplied to the hydrotreating step, a commercially available crude oil or a crude oil from which a naphtha fraction has been removed can be used. As such a crude oil, the preliminary distillation column is used. It is preferable to carry out desalting treatment in advance in order to prevent the inside from being contaminated and clogged, and to prevent deterioration of the hydrotreating catalyst. As a desalting method, a method generally used by those skilled in the art can be used, and examples thereof include a chemical desalting method, a petreco electric desalting method, and a How-Baker electric desalting method. .

When crude oil is treated in the preliminary distillation column as described above, the naphtha fraction and the fraction lighter than that are removed from the crude oil. In this case, the distillation conditions are usually
The temperature is in the range of 145 to 200 ° C., and the pressure is in the range of atmospheric pressure to 10 kg / cm ² , preferably 1.5 kg / cm.
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 latter stage, it is not necessary to distill it 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 usually has 5 to 10 carbon atoms. When the naphtha fraction is cut at a boiling point of less than 125 ° C, the hydrogen partial pressure may decrease during the hydrotreating process in the next step, which may reduce the efficiency of the hydrotreating process. If cut, the smoke point of the kerosene fraction obtained by the subsequent hydrotreatment and distillation tends to decrease.

The crude oil used in the present invention or the crude oil from which the naphtha content has been removed by the above-mentioned preliminary distillation method has a metal component consisting of at least one of vanadium, nickel and iron of 135 ppm by weight or less and an asphaltene content of 12% by weight or less. Those contained are preferably used. If the above 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 of more than 12% by weight are also not preferable because the catalyst life is remarkably shortened due to carbon precipitation.

The hydrorefining method of the present invention comprises:
Hydrodesulfurization is performed by contacting with a catalyst in the presence of hydrogen, 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 subjected to the catalyst in the presence of hydrogen. And hydrolyzing the gas component 1 and the effluent from the hydrocracking, and performing atmospheric distillation to obtain hydrocarbons having different boiling points.

The hydrodesulfurization used in the above hydrodesulfurization step
In the sulfurizer, crude oil or crude oil excluding naphtha fraction is removed.
The reaction conditions for hydrorefining oil are as follows:
Used. First, the reaction temperature is in the range of 300 to 450 ° C.
Is preferred. When the reaction temperature is lower than 300 ° C,
The reaction is extremely slow, and if it exceeds 450 ° C
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 to 420 ° C is more preferable. Also, the reaction pressure,
The hydrogen partial pressure is 30 to 200 kg / cm²A range of
Yes. The above pressure is 30 kg / cm²Solid when less than
Carbon deposits, catalyst life is significantly reduced, and 200k
g / cm²Pressures exceeding 10 are uneconomical in terms of device design. Up
For the same reason as described above, the hydrogen partial pressure is 100 to 180 kg /
cm²It is more preferable that the range is Furthermore, hydrogen /
Oil ratio is 300-2000Nm³/ Kiloliter range
Preferably there is. The above ratio is 300 Nm³/ Kiri
If it is less than 100 ton, hydrorefining does not proceed sufficiently, and 2
000 Nm³If it exceeds / kiloliter, design the device
It is uneconomical. For the same reason as above, the ratio is 5
00-1000Nm ³/ Kiloliter range
Is more preferable. Liquid hourly space velocity (LHSV) is 0.1 to 3.
0h^-1Is preferred. LHSV is 0.1h^-1Less than
If it is not, economically sufficient processing speed cannot be obtained, and it is 3.0h.
^-1If it exceeds the limit, the reaction time is insufficient and the feed oil is hydrogenated.
The drawback is that the purification is not completed. The same reason as above
Therefore, LHSV is 0.2-0.8h^-1The range of
Preferred.

The catalyst used in the hydrodesulfurization step is alumina, silica-alumina, or a mixture of alumina and at least one compound selected from boron and phosphorus as a carrier. , 9
Or, a catalyst carrying at least one selected from the metals belonging to Group 10 is preferably used, but as the metal belonging to Group 6 of the Periodic Table, tungsten and molybdenum are preferable, and the metals of Groups 8 to 10 of the Periodic Table are preferred. As the metal belonging to, nickel and cobalt are preferable. The Group 6 metal and the Group 8 to 10 metals may be used alone or in combination of two or more kinds of metals, but in particular, they have high hydrogenation activity and little deterioration. ,
Ni-Mo, Co-Mo, Ni-W, Ni-Co-Mo
A combination such as is preferable.

The amount of the metal carried is not particularly limited and may be appropriately selected according to various conditions.
Usually 1 to 35 as a metal oxide based on the total weight of the catalyst.
It is in the range of% by weight. If the supported amount is less than 1% by weight,
The effect as a hydrotreating catalyst is not sufficiently exerted, and when it exceeds 35% by weight, the hydrogenation activity is not significantly improved relative to the amount supported, and it is economically disadvantageous. In particular,
From the viewpoint of hydrogenation activity and economical efficiency, the range of 5 to 30% by weight is preferable.

As the above-mentioned catalyst, when a carrier obtained by adding at least one compound selected from boron and phosphorus to alumina is used as a carrier, a boron compound, a silicon compound or a phosphorus compound is respectively added based on the total weight of the carrier. Those containing 0.5 to 20% by weight are preferable. When the content is less than the lower limit value, the effect of improving the hydrogenation activity is small, and when the content exceeds the upper limit value, there is not much improvement effect of the hydrogenation activity for the amount,
In addition to being uneconomical, desulfurization activity may decrease, which is not preferable. In particular, the range of 1 to 18% by weight is preferable from the viewpoint of the effect of improving the hydrogenation activity.

The carrier is, for example, 60 to 100 ° C. obtained by adding a boron compound or a phosphorus compound in 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, and more preferably
After kneading by heating for 1.5 hours or more, it can be produced by molding, drying and baking by a known method. If the heating and kneading is less than 1 hour, the kneading may be insufficient and the dispersion state of boron atoms and the like may be insufficient. Further, if the kneading temperature deviates from the above range, the boron and the like may not be highly dispersed, Not preferable. The boron, silicon, phosphorus or each compound thereof may be added in a solution state by heating and dissolving in water, if necessary.

Here, the alumina precursor is not particularly limited as long as it can form alumina by firing, and for example, alumina hydrates such as aluminum hydroxide, pseudoboehmite, boehmite, bayerite and dibsite. Can be mentioned. The above-mentioned alumina or alumina precursor is preferably used with a water content of 65% by weight or more, and when the water content is less than 65% by weight, the dispersion of each compound such as phosphorus added may not be sufficient. .

As the boron compound, in addition to boron oxide, various boron compounds which can be converted into boron oxide by firing can be used. Examples thereof include boric acid, ammonium borate, sodium borate, and perborane. Sodium acid, orthoboric acid, tetraboric acid, boron pentasulfide, boron trichloride, ammonium perborate, calcium borate, diborane, magnesium borate, methyl borate, butyl borate, tricyclohexyl borate and the like can be mentioned. Further, among the above carriers, the phosphorus compound used in the carrier obtained by adding the phosphorus compound to alumina may include phosphorus alone. 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 their alkali metal salts or ammonium salts, pyrophosphoric acid, tripolyphosphoric acid and tetraphosphoric acid. 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, chalcogenized phosphorus, organic phosphoric acid, organic phosphoric acid Salt, etc. are mentioned. Of these, inorganic phosphoric acid having a low oxidation number and alkali metal salts or ammonium salts of condensed phosphoric acid are particularly preferable from the viewpoints of activity, water resistance and heat resistance, durability and the like.

As silica-alumina, for example, the molar ratio of silica to alumina is SiO ₂ / Al ₂ O ₃ is 3.5.
The above faujasite type zeolite and the like can be mentioned. Among these, the SiO ₂ / Al ₂ O ₃ molar ratio is 4.
It is preferably 6 or more from the viewpoint of heat resistance.

The average pore diameter of the above catalyst is 80 to 120.
The value in the range of Å is preferable, and the average pore diameter is 80.
If it is less than Å, the heavy molecules cannot sufficiently diffuse into the pores, the reaction becomes insufficient, and the properties of the residual oil (eg Ni, V
Content ratio). On the other hand, when it exceeds 120 Å, the surface area becomes small and the reaction does not proceed sufficiently. Further, in the present invention, the catalyst layer composed of the catalyst having the above composition is further divided into two stages, and the upstream side thereof is provided with 200
~ 5000Å, preferably a catalyst having an average pore size in the range of 1000-3000Å, 80-120Å on the downstream side.
From the viewpoint of catalyst life, it is more preferable to use a combination of catalysts having an average pore diameter of a certain degree.

In the present invention, the 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 preferably performed by using a high-pressure gas-liquid separation tank because it can be separated without largely changing the temperature and pressure of the effluent. In the hydrocracking apparatus used for hydrocracking treatment, the following conditions are used as the reaction conditions. First, the reaction temperature is 300 to 450.
The range of ° C is preferred. When the reaction temperature is lower than 300 ° C., the reaction progresses remarkably slow, and when it exceeds 450 ° C., overdecomposition progresses, and the yield of intermediate products 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 /
When it is less than cm ² , the properties of the produced middle distillate, such as hue and smoke point, are deteriorated, and the pressure exceeding 200 kg / cm ² is uneconomical in designing the apparatus. 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 300-2.
It is preferably in the range of 000 Nm ³ / kiloliter. If 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 if it exceeds 2000 Nm ³ / kL, it is uneconomical in the design of the apparatus. For the same reason as above,
More preferably, the above ratio is in the range of 500 to 1000 Nm ³ / kiloliter. LHSV is 0.1-3.0h
It is preferably in the range of ^-1 . When LHSV is less than 0.1 h ^-1, sufficient processing speed cannot be obtained from an economical point of view, and when it exceeds 3.0 h ^-1 , reaction time is insufficient and cracked oil yield is sufficiently obtained. I can't. For the same reason as above, LHSV is more preferably in the range of 0.2 to 0.8 h ^-1 .

The catalyst used in the hydrocracking treatment is, for example, No. 3 of Japanese Patent Publication No. 4-24106.
The generally known zeolitic residual oil cracking catalysts described in col. 18, line 18 to col. 6, line 30 can be used. Crystalline aluminosilicate, preferably iron-containing aluminosilicate, or a mixture of this and an inorganic oxide as a carrier, and at least one selected from metals belonging to Groups 6, 8, 9 and 10 of the Periodic Table It is possible to use a catalyst carrying. In particular, as the above carrier, iron-containing aluminosilicate 10 to 90% by weight and inorganic oxide 9
Those containing 0 to 10% by weight are preferable. When the content of iron-containing aluminosilicate in the carrier is less than 10% by weight, the effect as the hydrotreating catalyst is not sufficiently exerted,
On the other hand, if it exceeds 90% by weight, the effect of improving the hydrogenation activity is not so much seen for that amount, which is rather economically disadvantageous. In particular, from the viewpoint of hydrogenation activity and economical efficiency, iron-containing aluminosilicate 30 to 70% by weight and inorganic oxide 70 to 70% by weight are used.
It is preferably composed of 30% by weight.

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

In the present invention, the catalyst used in the hydrocracking treatment is selected from the metals obtained from the groups 6, 8, 9 and 10 of the periodic table for the carrier obtained as described above. Although at least one kind is supported, the supporting method is not particularly limited, and a known arbitrary method such as an impregnation method, a coprecipitation method, or a kneading method can be adopted. In addition, a desired metal is supported on the carrier at a predetermined ratio, and if necessary, dried and then fired. The firing temperature and time are appropriately selected depending on the type of the metal supported. Also, the periodic table
Alternatively, the metal belonging to Group 10 may be the same as that described in the hydrodesulfurization treatment. The hydrocracking catalyst thus obtained has an average pore size of 10
It is preferably 0 to 200Å. This average pore size is 10
If it is less than 0Å, the heavy molecule does not sufficiently diffuse into the pores, and the reaction does not proceed sufficiently. On the other hand, if it exceeds 200 Å, the surface area becomes small, and the reaction progresses insufficiently.

In the present invention, after the hydrodesulfurization, the high
Gas component 1 obtained by gas-liquid separation in a pressure-liquid separation tank
Can be further hydrorefined if necessary.
It In the hydrorefining equipment used in the above hydrorefining treatment
The following conditions are used as the reaction conditions. Well
The reaction temperature is preferably in the range of 300 to 450 ° C. Up
When the reaction temperature is lower than 300 ° C, the reaction progresses remarkably.
If the temperature exceeds 450 ° C, overdecomposition progresses.
However, due to the increase in gas yield, the yield of intermediate products declined
Already done. For the same reason as above, the reaction temperature is 3
The range of 60 to 420 ° C. is more preferable. Also, the reaction pressure
Force, that is, hydrogen partial pressure is 30 to 200 kg / cm ², 1 more
00-180kg / cm²Is preferred. Above pressure
Is 30 kg / cm²High pressure gas-liquid separation
It is economical to directly supply the gas component of the tank to the reactor
Therefore, the pressure of this process is
Determined by the conditions. Furthermore, the hydrogen / oil ratio is 200-2.
000 Nm³/ Kiloliter, further 500-1500N
m³It is preferably in the range of / liter. the above
Ratio is 200 Nm³/ Kiloliter is enough
However, the gas component of the high pressure gas-liquid separation tank is directly supplied to the reactor.
Hydrogen / oil in this process because it is economical to do
The ratio is determined by the hydrodesulfurization conditions in the preceding stage. LHS
V is 0.5-8.0h^-1It is preferably in the range of. LH
SV is 0.5h^-1If less than, it is sufficient from the economical point of view.
I couldn't get the speed, and it was 8.0h.^-1If it exceeds the time of reaction
Insufficient time to obtain sufficient yield of cracked oil. And above
For the same reason, LHSV is 1.0-5.0h^-1In the range of
More preferably.

The hydrorefining catalyst used in the hydrorefining treatment is alumina or silica, or a mixture of alumina and a compound of boron and / or phosphorus, or an iron-containing aluminosilicate as a carrier, and the periodic table. A catalyst carrying at least one selected from metals belonging to groups 6, 8, 9 and 10 is preferably used. As such a material, the same material as that used in the above hydrodesulfurization or hydrocracking treatment can be used. Such a hydrorefining catalyst preferably has an average pore size of 20 to 60Å. If the average pore size is less than 20Å, the diffusion resistance in the catalyst becomes large and the reaction does not proceed sufficiently. On the other hand, if it exceeds 60 Å, 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 subjected to the high pressure gas after hydrodesulfurization. 30 to 2 including the gas component 1 from the liquid separation tank
Under a pressure of 00 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 200 to
A method of contacting with a hydrorefining catalyst under the condition of 2000 Nm ³ / kL and combining it with the liquid hydrocarbon component 2 and carrying out atmospheric distillation can be preferably used. By adopting such a method, advantages such as improvement of smoke point of kerosene, improvement of hue of light oil, and improvement of cetane number can be obtained.

When the crude oil is directly hydrodesulfurized,
The reaction conditions are basically the same as those for hydrodesulfurization of crude oil excluding the naphtha fraction, but the hydrogen partial pressure decreases, so the hydrogen partial pressure and hydrogen / oil ratio are It is preferable to increase within the range. In this way,
Crude oil or crude oil excluding naphtha fraction is subjected to a batch hydrodesulfurization treatment, and this treated oil is then subjected to various products in an atmospheric distillation tower, such as naphtha fraction, kerosene fraction, gas oil fraction, atmospheric distillation residue. Etc. At this time, the operating conditions of the atmospheric distillation column are the same as the crude oil atmospheric distillation method that is widely used in petroleum refining equipment, and the normal temperature is about 300 to 380 ° C. and the pressure is atmospheric pressure to 1.0 kg / It is about cm ² G. By performing this step after the hydrodesulfurization step, heat recovery can be achieved and the operating cost can be greatly reduced. Further, in order to effectively use the existing crude oil atmospheric distillation column, the construction cost can be reduced by transferring the hydrodesulfurized oil to another refinery in another place and separating the product.

[0029]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Example 1 As the raw material oil, the one having the following properties excluding the naphtha fraction (C5 to 157 ° C.) of Arabian heavy desalted crude oil was used. Feedstock A Density (15 ° C) 0.9319 g / cm ³ Sulfur content 3.24 wt% Nitrogen content 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 wt% Gas oil fraction (higher than 239 ° C and lower than 370 ° C) 25.8 wt% Residual oil (higher than 370 ° C) 64.4 wt% As shown in Figure 1. In addition, the feed oil and hydrogen are supplied to a 1000 ml hydrodesulfurization reactor, the hydrodesulfurization reaction is performed using the catalyst A shown in Table 1, and the high pressure gas-liquid is maintained while maintaining the temperature and pressure after the reaction. The separated liquid component and hydrogen were supplied to a separation tank and then supplied to a 1000 ml hydrocracking apparatus, and hydrocracking was performed using the catalyst D shown in Table 1. The oil produced by the hydrocracking reaction and the above gas components were combined and subjected to atmospheric distillation. The reaction conditions of each reactor are shown in Table 2. In addition, the catalyst A shown in Table 1 has a
It is a generally known catalyst prepared by impregnating a water-soluble salt of the components shown in the table. The catalyst D is a generally known catalyst in which a mixture of iron-containing Y-type zeolite and alumina is used as a carrier and a metal salt is impregnated from an aqueous solution. The obtained hydrotreated oil was distilled to obtain a naphtha fraction (C5 to 157 ° C or less), a kerosene fraction (higher than 157 ° C and 239 ° C or less), and a gas oil fraction (2
Fractional distillation was conducted into a residual oil (higher than 370 ° C. and higher than 39 ° C.) and a residual oil (higher than 370 ° C.) to determine the respective properties. Also,
A storage stability test was conducted 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 light oil fraction was conducted with a vent.
400 ml of the sample was put 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 understood that kerosene having a good smoke point and gas oil having a good cetane number are obtained because the middle distillate rich in paraffin is produced by the hydrocracking of residual oil.

Example 2 As a raw material oil, Arabian light desalted crude oil having the following properties was used. Feedstock B Density (15 ° C) 0.86339 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 (higher than 157 ° C and lower than 239 ° C) 14.2% by weight light oil fraction (higher than 239 ° C and lower than 370 ° C) 25.6% by weight residual oil (370 ° C) Higher) 45.5 wt% As shown in FIG. 1, feed oil and hydrogen were supplied to a 1000 ml hydrodesulfurization reactor, and the hydrodesulfurization reaction was performed using the 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, the separated liquid component and hydrogen were supplied to a 1000 ml hydrocracker, and hydrogen was produced using catalyst D shown in Table 1. Chemical decomposition was performed. The oil produced by the hydrocracking reaction and the above gas components were combined and subjected to atmospheric distillation. The reaction conditions of each reactor are shown in Table 2. In addition, the catalyst C shown in Table 1 is the first on the alumina carrier.
It is a generally known catalyst prepared by impregnating a water-soluble salt of the components shown in the table. The catalyst D is a generally known catalyst in which a mixture of iron-containing Y-type zeolite and alumina is used as a carrier and a metal salt is impregnated from an aqueous solution. In the same manner as in Example 1,
The obtained hydrotreated oil was distilled, and the properties of each obtained fraction were determined. In addition, a storage stability test was conducted on the kerosene fraction and the gas oil fraction. The results are shown in Tables 3 and 4. It was found that, even when Arabian light desalted crude oil was used as the raw material oil, it was possible to increase the production of middle distillates having good properties as in Example 1.

Example 3 As shown in FIG. 2, feed oil B and hydrogen were fed to a 1000 ml hydrodesulfurization reactor, and catalyst B shown in Table 1 was used.
Is subjected to a hydrodesulfurization reaction, and while maintaining the temperature and pressure after the reaction, it is supplied to a high pressure gas-liquid separation tank, and the separated liquid component and hydrogen are supplied to a 1000 ml hydrocracker, Hydrocracking was carried out using catalyst D shown in Table 1. On the other hand, the gas component obtained in the high-pressure gas-liquid separation tank is used as a catalyst E in a 100 ml hydrorefining reactor.
Contact with. The product oil from the hydrocracking and the gas component from the hydrorefining were combined and subjected to atmospheric distillation. The reaction conditions of each reactor are shown in Table 2. 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 components shown in Table 1. Also,
Catalyst D is a generally known catalyst in which a mixture of iron-containing Y-type zeolite and alumina is used as a carrier and a metal salt is impregnated from an aqueous solution. The hydrotreated oil obtained was distilled in the same manner as in Example 1, and the properties of each of the obtained fractions were determined. In addition, a storage stability test was conducted 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 better properties was obtained.

Example 4 As shown in FIG. 3, feed oil A and hydrogen were fed to a 1000 ml hydrodesulfurization reactor, and catalyst B shown in Table 1 was used.
Is used to perform a hydrodesulfurization reaction, and while maintaining the temperature and pressure after the reaction, the high pressure gas-liquid separation tank 1 is supplied, and the separated liquid component 1 and hydrogen are supplied to a 1000 ml hydrocracking reactor. Then, hydrogenolysis was performed using the catalyst D shown in Table 1. Further, the effluent after the hydrocracking reaction is kept in the high pressure gas-liquid separation tank 2 while maintaining the temperature and pressure, and the liquid component 2
And gas component 2 were separated. On the other hand, the gas components 1 and 2 obtained in the high-pressure gas-liquid separation tanks 1 and 2, respectively, are combined into 1
The catalyst F was contacted in a 00 ml 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.
In addition, a storage stability test was conducted 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 and light oil with even better properties in kerosene smoke point and light oil hue were obtained.

Comparative Example 1 As shown in FIG. 4, the feed oil A was hydrotreated 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 fractionally distilling 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 are shown in Tables 3 and 4. Shown in the table. It can be seen that when only hydrodesulfurization is performed in the crude oil batch treatment, the quality is insufficient in all of the metal amount and nitrogen amount of the residual oil, the hue and smoke point of kerosene and light oil, and the cetane index.

Comparative Example 2 As shown in FIG. 5, the raw material oil B was directly fed to the hydrocracking apparatus without gas-liquid separation in 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 fractionally distilling 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 are shown in Tables 3 and 4. Shown in the table. When light fractions are also supplied to the hydrocracking reactor at the same time without gas-liquid separation, the paraffin content in kerosene oil is decomposed more than the decomposition of heavy fractions. However, the quality such as light oil cetane number will decrease.

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

[Table 3]

[0038]

[Table 4]

[0039]

According to the present invention, in a batch hydrodesulfurization process of crude oil or crude oil excluding naphtha fraction, by obtaining a highly saturated intermediate fraction by hydrocracking of residual oil,
In addition to hydrodesulfurization of heavy oil, it is possible to effectively carry out hydroreforming of light kerosene, increase production of high-quality light kerosene, and simplify refining equipment.

[Brief description of drawings]

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

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

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

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

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

Claims (8)

[Claims] 1. A crude oil or a crude oil from which a naphtha fraction has been removed is brought into contact with a catalyst in the presence of hydrogen 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. The liquid hydrocarbon component 1 is separated and hydrocracked by contacting it with a catalyst in the presence of hydrogen, and then the gas component 1 and the effluent from the hydrocracking are combined and subjected to atmospheric distillation to remove the boiling point. A method for hydrorefining crude oil or crude oil excluding naphtha fraction, which comprises obtaining different hydrocarbons. 2. Hydrodesulfurization is performed at 30 to 200 kg / cm.sup.2.
Under the pressure of ² , at a temperature of 300 to 450 ° C., the LHSV is 0.
^{1 to} 3.0 h ^-1 , hydrogen / oil ratio of 300 to 2000 Nm ³ /
The hydrorefining method according to claim 1, wherein the hydrorefining method is carried out under the condition of kiloliters. 3. A catalyst used for hydrodesulfurization is alumina, silica-alumina, or a mixture of alumina and at least one compound selected from boron and phosphorus as a carrier. 2. The hydrorefining method according to claim 1, which carries at least one selected from the group 10 metals. 4. Hydrocracking is performed at 30 to 200 kg / cm.
Under the pressure of ² , at a temperature of 300 to 450 ° C., the LHSV is 0.
^{1 to} 3.0 h ^-1 , hydrogen / oil ratio of 300 to 2000 Nm ³ /
The hydrorefining method according to claim 1, wherein the hydrorefining method is carried out under the condition of kiloliters. 5. A catalyst used for hydrocracking is selected from metals belonging to Groups 6, 8, 9 or 10 of the Periodic Table in a carrier composed of crystalline aluminosilicate or a mixture of crystalline aluminosilicate and inorganic oxide. The hydrorefining method according to claim 1, which carries at least one of the following: 6. The gas component which is subjected to atmospheric distillation together with the effluent from the hydrocracking is further separated from the gas component 1 separated in the high pressure gas-liquid separation tank under a pressure of 30 to ²⁰⁰ kg / cm ² .
LHSV of 0.5-8.0 at 300-450 ℃
2. The hydrorefining method according to claim 1, which is obtained by contacting with a hydrorefining catalyst under the conditions of h ⁻¹ and hydrogen / oil ratio of 200 to 2000 Nm ³ / kil. 7. The hydrorefining catalyst comprises alumina, silica,
Silica-alumina or a material obtained by adding at least one compound selected from boron and phosphorus to alumina, and carrying 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. The 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 together with the gas component 1 is 30 to 200 kg.
LHS at a temperature of 300 to 450 ° C. under a pressure of / cm ^2.
V is 0.5-8.0h ^-1 , hydrogen / oil ratio is 200-2000N
The hydrorefining method according to claim 1, wherein what is brought into contact with the hydrorefining catalyst under the condition of m ³ / kilitter is combined with the liquid hydrocarbon component 2 and subjected to atmospheric distillation.