JP6812265B2 - How to treat pyrolyzed heavy light oil - Google Patents

Description

The present invention relates to a method for treating heavy oil. More specifically, the present invention relates to a method for treating heavy oil, which efficiently treats thermally decomposed heavy light oil obtained from a heavy oil pyrolysis apparatus that thermally decomposes vacuum distillation residual oil and the like.

In recent years, the demand for petroleum products has tended to be lighter, and in petroleum refining, it is required to produce more light oils such as gasoline, kerosene and light oil.
For this reason, it is required that vacuum distillation residual oil, which has been mainly used as a raw material for heavy oil and asphalt, is further subjected to thermal cracking and catalytic cracking to increase the yield of light oil.

As a method for producing light oil from vacuum distillation residual oil, the vacuum distillation residual oil is introduced into a heavy oil thermal decomposition apparatus and thermally decomposed, and the obtained decomposed naphtha and decomposed gas oil are hydrogenated and desulfurized to desulfurize. Examples thereof include a method of producing naphtha, desulfurized kerosene, desulfurized gas oil and the like, and using these as raw materials for each gas oil. For example, Patent Document 1 describes that a vacuum distillation residual oil is used as a thermal decomposition raw material oil for thermal decomposition and further hydrodesulfurized.

In the thermal decomposition in the heavy oil pyrolysis apparatus, the thermally decomposed heavy light oil can be obtained together with the decomposed naphtha and the decomposed gas oil. Although heavy gas oil fractions are useful as raw materials for heavy oil, since the demand for heavy oil is declining, it is required to increase the yield of light oil from pyrolyzed heavy oil. Therefore, the thermally cracked heavy oil obtained from the heavy oil cracking apparatus is hydrocracked, and light components such as desulfurized kerosene and desulfurized gas oil generated by the hydrodesulfurization are used as raw materials for each gas oil. Desulfurized heavy light oil obtained by hydrogenated desulfurization is further used as a part of a raw material for fluid cracking.
Under these circumstances, the emergence of economical methods to further increase the yield of light oil has been sought.

JP-A-2015-151431

An object of the present invention is to provide a method for efficiently and economically treating heavy oil. Specifically, it provides a method for treating heavy oil, which treats thermally decomposed heavy light oil obtained from a heavy oil pyrolysis apparatus by a simple method and increases the treatment efficiency and the yield rate of light oil as a whole. The challenge is to do.

The present invention relates to the following matters.
[1] Steps 1 of introducing heavy oil into the heavy oil thermal decomposition apparatus (A) and performing thermal decomposition to obtain a fraction (a) containing thermally decomposed heavy light oil.
Step 2 to obtain desulfurized heavy gas oil (b) by introducing the fraction (a) containing the pyrolysis heavy gas oil obtained in step 1 into the pyrolysis oil desulfurization apparatus (B) and performing hydrodesulfurization. When,
The step 3 of introducing at least a part of the desulfurized heavy light oil (b) obtained in the above step 2 into the fluid cracking apparatus (C) and performing catalytic cracking to obtain the catalytic cracking heavy oil (c). Have and
At least a part of the catalytically cracked heavy gas oil (c) obtained in the step 3 is introduced into the pyrolyzed oil desulfurization apparatus (B) together with the fraction (a) containing the pyrolyzed heavy gas oil, and the step. A method for treating heavy oil, which comprises performing 2.
[2] The treatment of the heavy oil according to the above [1], wherein the raw material oil to be introduced into the fluidized catalytic cracking apparatus (C) contains the desulfurized reduced pressure gas oil together with the desulfurized heavy oil (b). Method.
[3] The fraction (a) containing the thermally decomposed heavy light oil is characterized by having a 30% distillate temperature of 400 to 430 ° C. and a 90% distillate temperature of 500 to 530 ° C. [1]. ] Or [2]. The method for treating heavy oil.
[4] The catalytically cracked heavy light oil (c) introduced into the pyrolysis oil desulfurization apparatus (B) has a 30% distillation temperature of 370 to 400 ° C. and a 90% distillation temperature of 410 to 440 ° C. The method for treating heavy oil according to any one of the above [1] to [3].
[5] The weight according to any one of the above [1] to [4], wherein the hydrodesulfurization in the step 2 is carried out under the conditions of a reaction temperature of 250 to 450 ° C. and a hydrogen partial pressure of 3 to 20 MPa. How to treat oil.

According to the heavy oil treatment method of the present invention, heavy oil is treated by a simple method without drastically changing the equipment configuration, and the yield of light oil is increased, which is economical and efficient. Driving can be achieved.

FIG. 1 shows an example of a flow chart of heavy oil treatment according to the present invention.

Hereinafter, the present invention will be specifically described.
The method for treating heavy oil of the present invention is
Step 1 (pyrolysis step) of introducing heavy oil into the heavy oil thermal decomposition device (A) and performing thermal decomposition to obtain thermal decomposition heavy light oil.
Step 2 (desulfurization step) in which the pyrolysis heavy gas oil obtained in step 1 is introduced into the pyrolysis oil desulfurization apparatus (B) and hydrodesulfurized to obtain desulfurized heavy gas oil.
It has a step 3 (contact cracking step) of introducing at least a part of the desulfurized heavy gas oil obtained in the step 2 into a fluid cracking apparatus (C) and performing catalytic cracking to obtain a catalytic cracking heavy gas oil. ..

Process 1 (pyrolysis process)
In step 1 according to the present invention, heavy oil, which is a pyrolysis raw material oil, is introduced into a heavy oil pyrolysis apparatus (A) and pyrolyzed to obtain a fraction (a) containing pyrolyzed heavy light oil. It is a pyrolysis process.
The heavy oil used in step 1 is a thermal decomposition raw material oil that is thermally decomposed by the heavy oil thermal decomposition apparatus (A), and is not particularly limited, but is an atmospheric distillation residual oil and a reduced pressure distillation residual oil. , Other heavy oils, and mixed oils in which two or more of these are mixed. The atmospheric distillation residual oil is not particularly limited, and is the residue after atmospheric distillation of crude oil and separation of evaporation fractions. The vacuum distillation residual oil is not particularly limited, and is the residue after atmospheric distillation of the atmospheric distillation residual oil and separating the evaporated fraction. As other heavy oils, heavy hydrocarbon oils other than atmospheric pressure distilled residue oil and vacuum distillation residual oil can be used without particular limitation. For example, catalytic cracking heavy light oil obtained from a fluid cracking apparatus, Examples thereof include slurry oil obtained from a fluidized catalytic cracking apparatus, residual oil of ethylene crackers, and the like.

When the heavy oil to be subjected to step 1 is a mixed oil of two or more kinds of heavy oils selected from atmospheric distillation residual oil, vacuum distillation residual oil and other heavy oils, the mixing ratio thereof is particularly limited. It is not adjusted as appropriate.

In the present invention, the atmospheric distillation residual oil, the vacuum distillation residual oil, and the crude oil used as the raw material of the other heavy oils used as the components of the heavy oil used in the step 1 are not particularly limited, and any crude oil is distilled. It may be obtained by using it as a raw material. Crude oil species are not particularly limited, but for example, Arabian Heavy, Arabian Medium, Arabian Light, Arabian Extra Light, Kuwait, Basra, Oman, Marvan, Mubaras Blend, Zakum, Upper Zakum, Qatar Land, Qatar Marine, Umshaif, Silly, Examples include Khafji, Espo, etc., and may be any one type or a combination of two or more types.

In the present invention, as the heavy oil to be used in step 1, the total content of the atmospheric distillation residual oil and the vacuum distillation residual oil is preferably 40% by volume or more, more preferably 70% by volume or more. More preferably, it is preferable to use a heavy oil containing 40% by volume or more, more preferably 70% by volume or more of the vacuum distillation residual oil.

In step 1, heavy oil, which is a thermal decomposition raw material oil, is introduced into the heavy oil thermal decomposition apparatus (A) to perform thermal decomposition. As the conditions for this pyrolysis treatment, the thermal decomposition temperature is preferably 490 to 510 ° C., particularly preferably 495 to 505 ° C., and the pressure (gauge pressure) during the thermal decomposition treatment is preferably 0. It is 01 to 0.6 MPaG, particularly preferably 0.05 to 0.4 MPaG. Also, the atmosphere of the pyrolysis treatment is steam. In addition, if excessive foaming is observed during the thermal decomposition treatment, an antifoaming agent may be added. As the defoaming agent, a silicon-based defoaming agent or the like can be generally used.

In step 1, when heavy oil, which is a pyrolysis raw material oil, is thermally decomposed by a pyrolysis apparatus, a pyrolysis product is produced. Therefore, from this pyrolysis product, the boiling point range is usually 170 to 600 ° C., preferably the boiling point. A fraction having a range of 200 to 570 ° C. is fractionated and distilled from a pyrolysis apparatus, and the fraction is obtained as a pyrolysis treatment oil. The sulfur content of the pyrolysis treatment oil is preferably 2 to 6% by mass, the nitrogen content is preferably 0.5 to 6% by mass, and the residual carbon is preferably 0.1 to 4% by mass. This pyrolysis-treated oil contains a fraction (a) containing a pyrolysis heavy light oil, and can be used for hydrodesulfurization in step 2 described later. The entire pyrolysis-treated oil may be collectively subjected to hydrodesulfurization in step 2, or may be fractionated into two or more fractions depending on the boiling point, and each of them may be subjected to hydrodesulfurization.

In the present invention, preferably, the thermal decomposition product obtained from the heavy oil thermal decomposition apparatus (A) is used as a fraction (a) containing thermally decomposed heavy light oil and a light fraction such as decomposed naphtha / decomposed gas oil. It is desirable to divide each of them into hydrodesulfurization and subject them to hydrodesulfurization. For example, only the decomposed heavy gas oil fraction having a boiling point range of about 200 to 560 ° C. is heated as the fraction (a) containing the thermally decomposed heavy gas oil. It can be introduced into the cracked oil desulfurization apparatus (B) and subjected to hydrodesulfurization in step 2, and the fractions of the cracked naphtha and the cracked gas oil can be introduced into separate thermally cracked oil desulfurization apparatus for hydrodesulfurization.

In the present invention, the fraction (a) containing the pyrolysis heavy gas oil to be introduced into the pyrolysis oil desulfurization apparatus (B) preferably has a 30% distillation temperature of 350 to 450 ° C. and a 90% distillation temperature. The fraction is 480 to 550 ° C., more preferably the fraction has a 30% distillation temperature of 400 to 430 ° C. and a 90% distillation temperature of 500 to 530 ° C.
Of the pyrolysis products, those excluding the pyrolysis-treated oil can be used as a raw material for petroleum coke.

Step 2 (desulfurization step)
In step 2 according to the present invention, the fraction (a) containing the pyrolysis heavy gas oil obtained in the step 1 is introduced into the pyrolysis oil desulfurization apparatus (B) to perform hydrodesulfurization, and the desulfurized heavy material is carried out. This is a desulfurization process for obtaining light oil.

In the present invention, at least a part of the catalytically cracked heavy gas oil (c) obtained in step 3 described later is introduced into the pyrolysis oil desulfurization apparatus (B) together with the fraction (a) containing the cracked heavy gas oil. Perform hydrodesulfurization. That is, the desulfurization raw material oil hydrodesulfurized in step 2 is a distillate (a) containing the thermally cracked heavy gas oil obtained in step 1 and at least a part of the catalytically cracked heavy gas oil (c). contains. The ratio of the catalytically cracked heavy light oil (c) obtained in step 3 to be introduced into the pyrolysis oil desulfurization apparatus (B) is not particularly limited, but is usually 40% by volume or more, preferably 40% by volume or more. It is 60% by volume or more, more preferably 80% by volume or more, and the entire amount may be introduced into the pyrolysis oil desulfurization apparatus (B).

In step 2, a desulfurization raw material oil containing a fraction (a) containing a thermally cracked heavy gas oil and at least a part of a catalytically cracked heavy gas oil (c) is hydrogenated under high temperature pressurization and in the coexistence of a desulfurization catalyst. Chemical desulfurization.
The desulfurization catalyst used in step 2 is a refractory inorganic oxide carrier on which a hydrogenation active component is supported. As the fire-resistant inorganic oxide carrier of the desulfurization catalyst, a single substance or a mixture of alumina, silica, titania, magnesia and the like is used, or further, various oxides such as zirconia, boron oxide and zinc oxide and Y zeolite are used. A mixture of various zeolites such as ZSM-5 zeolite is used. The hydroactive components carried on the desulfurization catalyst include group 6 elements in the long periodic table such as molybdenum and tungsten, and group 9 and group 10 elements in the long periodic table such as cobalt and nickel. Is used, and if necessary, phosphorus, iron, platinum, etc. are used in addition to these metals.

The average pore diameter of the desulfurization catalyst is not particularly limited, but is preferably 5 to 15 nm, particularly preferably 6 to 12 nm. When the average pore diameter of the desulfurization catalyst is in the above range, it has stable metal resistance and it is easy to obtain sufficient desulfurization performance. The specific surface area of the desulfurization catalyst is preferably 150 to 350 m ² / g, particularly preferably 200 to 320 m ² / g. When the specific surface area of the desulfurization catalyst is in the above range, it becomes easy to obtain sufficient desulfurization performance. Further, the volume occupied by the pores having an average pore diameter of ± 1.5 nm of the desulfurization catalyst is preferably 50% or more, particularly preferably 60% or more of the total pore volume. When the volume occupied by the pores having an average pore diameter of ± 1.5 nm of the desulfurization catalyst is within the above range, it becomes easy to obtain sufficient desulfurization activity.

In step 2, hydrodesulfurization can also be performed after demetallizing, if necessary, using a demetallizing catalyst for removing metal components from the desulfurization raw material oil. For example, a demetallizing catalyst for removing metal from the desulfurization raw material oil is filled in the first stage, a desulfurization catalyst is filled in the subsequent stage, and the raw material oil is sequentially supplied to each catalyst bed to perform demetallization and hydrodesulfurization. be able to.

The demetallization catalyst is a fire-resistant inorganic oxide carrier on which a hydrogenation active component is supported, and effectively removes metals from raw materials oil containing heavy metals such as sulfur, asphaltene, and nickel and vanadium. In order to do so, the front part of the catalyst bed is filled. As the fire-resistant inorganic oxide carrier of the demetallizing catalyst, a single substance or a mixture of alumina, silica, alumina-silica, etc. is used, or a mixture of these with various metals such as boron oxide and zinc oxide is used. Used. Group 6 elements in the long periodic table such as molybdenum and tungsten, group 9 elements and group 10 elements in the long periodic table such as cobalt and nickel are examples of the hydroactive components carried on the demetallization catalyst. Used.

The average pore diameter of the demetallizing catalyst is preferably 15 to 25 nm, particularly preferably 18 to 23 nm. When the average pore diameter of the demetallizing catalyst is in the above range, sufficient demetallizing activity can be easily obtained, and hydrogenation activity and catalyst strength tend to be high. The pore volume of the demetallizing catalyst is preferably 0.6 to 0.8 ml / g, particularly preferably 0.65 to 0.8 ml / g. When the pore volume of the demetallized catalyst is in the above range, it has a sufficient catalyst life and catalyst strength, and stable operation is facilitated.

The catalyst strength of the desulfurization catalyst and the demetallization catalyst is SCS (Side Compressing Strength), preferably 9 N / mm or more, and particularly preferably 13 N / mm or more. The SCS is a value obtained by laying the catalyst horizontally, applying a load, determining the load mass at which the catalyst is destroyed, and dividing by the catalyst length, and indicates the fracture strength per unit length of the catalyst. When the SCS of the desulfurization catalyst and the demetallization catalyst is in the above range, the catalyst cracking in the reactor is less likely to occur, and continuous operation is facilitated.

The demetallization catalyst and the desulfurization catalyst may be a new catalyst or a regeneration catalyst. The ratio of the desulfurization catalyst to the demetallization catalyst is appropriately selected according to the operating conditions, and the higher the ratio of the demetallization catalyst, the higher the effect of preventing the activity deterioration due to the metal, and the higher the ratio of the desulfurization catalyst. The higher the desulfurization activity, the higher the desulfurization activity.

The conditions for hydrodesulfurization in step 2 are appropriately selected in consideration of the target sulfur content of the desulfurized oil to be obtained in step 2 and the activity of the desulfurization catalyst.
The reaction temperature of hydrodesulfurization in step 2 is preferably 250 to 450 ° C., particularly preferably 300 to 400 ° C., and the partial pressure of hydrogen is preferably 3 to 20 MPa, more preferably 5 to 17 MPa, particularly preferably 8. It is ~ 15 MPa. Hydrogen / oil ratio is preferably ^{1000~3000m 3 (normal) / m 3} , particularly preferably ^{1500~2500m 3 (normal) / m 3} , the liquid space velocity is preferably 0.1～3.0H ^{- 1} , particularly preferably 0.15 to 2.0 h ^-1 .

When the reaction temperature of hydrodesulfurization is within the above range, the activity of the desulfurization catalyst is easily exhibited, and the thermal decomposition of the raw material oil does not proceed too much, so that hydrodesulfurization can be smoothly performed, and desulfurization can be easily performed. It becomes easy to suppress the deterioration of the activity of the catalyst. When the hydrogen partial pressure of hydrodesulfurization is within the above range, the hydrogenation reaction can easily proceed sufficiently, and it becomes easy to avoid an increase in equipment construction cost and operation cost. When the hydrogen / oil ratio of hydrodesulfurization is in the above range, the activity of the desulfurization catalyst is likely to be exhibited, and the economic efficiency is likely to be high. When the liquid space velocity of hydrodesulfurization is in the above range, it is easy to secure economic efficiency and the activity of the desulfurization catalyst is easily exhibited.

The sulfur content in the desulfurized oil obtained in step 2 is preferably 0.3% by mass or less. When the sulfur content in the desulfurized oil is within the above range, it can be suitably used as a raw material for the fluid cracking apparatus (C) in step 3 described later, and in some cases, a part of it is a base material of heavy oil C. It can also be used as.

In step 2, hydrodesulfurization is performed under high temperature and high pressure conditions as described above, so that the desulfurization raw material oil is the thermally cracked heavy gas oil (a) obtained in step 1 and the catalytically cracked heavy gas oil obtained in step 3. Even when it is composed of only (c), the hydrodesulfurized oil usually contains hydrodesulfurized gas oil (b) as well as light components such as hydrodesulfurized gas oil, hydrodesulfurized kerosene, hydrodesulfurized naphtha, and gas components.

In the present invention, the yield of the light component in step 2 is unexpectedly higher than that in the case where the catalytically cracked heavy light oil (c) obtained in step 3 is not introduced into step 2.
Of the desulfurized oil obtained in step 2, at least a part of the desulfurized heavy light oil (b) having a boiling point range of about 200 to 560 ° C. is subjected to step 3.

Step 3 (contact cracking step)
In step 3 of the present invention, at least a part of the desulfurized heavy light oil (c) obtained in step 2 is introduced into a fluid cracking apparatus (FCC apparatus) (C) to perform catalytic cracking, and catalytic cracking weight is performed. This is a catalytic cracking step of obtaining a catalytic cracking oil containing the quality oil (c).

In step 3, of the desulfurized oils obtained in step 2, for example, only the desulfurized heavy light oil (c) having a boiling point range of about 200 to 560 ° C. is introduced into the fluid cracking apparatus (C) as a catalytic cracking raw material. Alternatively, the desulfurized heavy light oil (c) and other hydrocarbon oil may be introduced into the fluid cracking apparatus (C). That is, in step 3, other hydrocarbon oil may be used as the catalytic cracking raw material oil together with the desulfurized heavy light oil (c).

As the other hydrocarbon oil, a heavy oil that has been hydrodesulfurized and hydrodecomposed in advance is preferably used, and examples thereof include indirect desulfurized heavy oil and direct desulfurized heavy oil. Examples of the indirect desulfurized heavy oil include desulfurized reduced pressure light oil obtained by desulfurizing a heavy light oil and a reduced pressure light oil obtained by atmospheric distillation of crude oil with an indirect desulfurization apparatus. Further, the indirect desulfurized heavy oil and the desulfurized oil obtained from the solvent stripping device may be used in combination as the raw material oil. On the other hand, as direct desulfurization heavy oil, for example, high-density petroleum distillates such as atmospheric distillation residual oil and vacuum distillation residual oil of crude oil, heavy gas oil, catalytic cracking residual oil, bisbraking oil and bitumen are directly desulfurized. Examples thereof include hydrodesulfurized and desulfurized heavy oil obtained by hydrocracking in an apparatus. As the other hydrocarbon oil, among these, desulfurized reduced pressure gas oil obtained by desulfurizing the vacuum light oil obtained from the vacuum distillation apparatus can be preferably used.

In the present invention, of the 100% by volume of the catalytic cracking raw material oil introduced into the fluid cracking apparatus (C) in step 3, the desulfurized heavy light oil (c) obtained in step 2 is preferably 10% by volume or more, more preferably. Is preferably contained in an amount of about 15 to 40% by volume.

The flow catalytic cracking apparatus (C) is an apparatus having a reaction tower for cracking the raw material oil by contacting the catalyst with the catalytic cracking raw material oil and a regeneration tower for regenerating the catalyst, and known ones can be used. it can. In the fluidized catalytic cracking apparatus (C), the raw material oil is brought into contact with the catalyst to decompose the raw material oil, the decomposition product and the catalyst are separated in the reaction tower, the separated catalyst is transferred to the regeneration tower, and the inside of the regeneration tower is used. The coke on the catalyst is burned in the catalyst to regenerate the catalyst, and the regenerated catalyst is used again for cracking the catalytic cracking feedstock.

The catalyst used in the fluid cracking apparatus (C) contains 10 to 75% by mass of clay mineral, 20 to 60% by mass of crystalline aluminosilicate, and 5 to 40% by mass of an alumina binder. A catalytic cracking catalyst of a hydrocarbon oil characterized in that the average particle size of the clay mineral is 1 μm or less and the particle size of 90% by mass is 2 μm or less is known (for example, Japanese Patent Application Laid-Open No. 2008-173583). reference). By using such a catalytic cracking catalyst, FCC gasoline can be obtained in high yield.

The operating conditions of the flow catalytic cracking apparatus (C) are appropriately adjusted in consideration of the type and amount of raw material oil, the type and amount of catalyst, the yield of the target product, the state of the catalyst introduced into the regeneration tower, and the like. You can decide. Therefore, the operating conditions of the flow catalytic cracking apparatus (C) are not particularly limited, but for example, the outlet temperature of the reaction tower 20 is preferably 450 ° C. or higher and 550 ° C. or lower, more preferably 470 ° C. or higher. Conditions of 540 ° C. or lower, more preferably 490 ° C. or higher and 530 ° C. or lower can be adopted. Further, in the regeneration tower, the used catalyst and air are introduced to burn the cork on the catalyst to regenerate the used catalyst. For example, the inside of the regeneration tower is operated at a temperature of 640 to 800 ° C. be able to.

In the reaction column of the catalytic cracking apparatus (C), cracking products containing the catalytic cracking heavy light oil (c) are produced. The decomposition products are usually washed and purified by an attached distillation column, separated into each fraction, and discharged. Separation of each fraction is carried out according to desired product properties, and is not particularly limited, for example, fuel gas, liquefied petroleum gas (LPG), naphtha, gasoline, catalytic cracked gas oil (LCO), catalytic cracking weight. It is separated into fractions such as quality light oil (c) and catalytic cracking bottom oil (slurry oil).

In the present invention, at least a part of the catalytically cracked heavy light oil (c) is introduced into the above-mentioned pyrolysis oil desulfurization apparatus (B) to perform step 2.
The catalytically cracked heavy light oil (c) introduced into the pyrolysis oil desulfurization apparatus (B) preferably has a 30% distillate temperature of 330 to 430 ° C. and a 90% distillate temperature of 400 to 460 ° C. More preferably, the fraction has a 30% distillation temperature of 370 to 400 ° C. and a 90% distillation temperature of 410 to 440 ° C.

In the present invention, in treating heavy oil by the above-mentioned steps 1 (thermal cracking step), step 2 (desulfurization step) and step 3 (contact cracking step), the catalytic cracking heavy oil (c) obtained in step 3 At least a part of the above is introduced into the thermally cracked oil desulfurization apparatus (B) together with the distillate (a) containing the thermally cracked heavy gas oil obtained in the step 1 to perform the step 2. The catalytic cracking heavy light oil (c) is usually obtained by using catalytic cracking raw material oil that has undergone a desulfurization step at least once, but is further cracked by introducing it into step 2 in which the reaction is carried out under high temperature and high pressure conditions. Is considered to occur, resulting in a change in the yield of light oil.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.
In the following examples and comparative examples, the density is JIS K 2249-1 "Crude oil and petroleum products-Density test method and density / mass / capacity conversion table (vibration type density test method)", and the sulfur content is JIS K 2541. -4 "Crude oil and petroleum products-Sulfur content test method Part 4: Radial excitation method", Nitrogen content is JIS K 2609 "Crude oil and petroleum products-Nitrogen content test method", Distillation properties are JIS K 2254 "Petroleum products" -Distillation test method (gas chromatograph method distillation test method) ".

The contents of nickel and vanadium conformed to the Petroleum Society Standard JPI-5S-62-2000 "Petroleum Product Metal Analysis Test Method (ICP Emission Analysis Method)".
Aromatic composition, naphthenic, the percentage of saturation is meant a method in accordance with ASTM D 3238-85, respectively (n-d-M ring analysis) by sought% C _A,% C _N, the% C _P.

[Example 1]
According to the flow of FIG. 1, heavy oil was treated by an apparatus configuration including a heavy oil pyrolysis apparatus (A), a thermal cracking oil desulfurization apparatus (B), and a fluidized catalytic cracking apparatus (C).

(Step 1)
The vacuum distillation residual oil 1 derived from crude oil produced in the Middle East and the slurry oil discharged from the fluidized catalytic cracking apparatus (C) described later are introduced into the heavy oil thermal cracking apparatus (A) as the thermal cracking raw material oil 1 at 500 ° C. , 0.1 MPaG (gauge pressure) was subjected to a pyrolysis treatment to obtain a pyrolyzed heavy light oil a-1 and other distillates. Table 1 shows the properties of the pyrolyzed heavy light oil a-1.

(Step 2)
The thermally cracked heavy gas oil a-1 (introduced flow rate: 1157 KL / D) obtained in step 1 and the catalytically cracked heavy oil c-1 (introduced flow rate: 78 KL / D) obtained in step 3 described later are merged. , Introduced into a thermally cracked oil desulfurization apparatus (B) as desulfurization raw material oil 1, reaction temperature is 350 ° C, hydrogen partial pressure is 13.0 MPa, hydrogen / oil ratio is 1,200 m ³ (normal) / m ³ , liquid space. Hydrodesulfurization treatment was carried out under the condition of a rate of 0.25 h ^-1 to obtain desulfurized heavy gas oil b-1 and other distillates. Table 2 shows the properties of desulfurized heavy gas oil b-1.

The thermal decomposition oil desulfurization apparatus (B) includes a first bed: NiMo / CoMo desulfurization catalyst, a second bed: CoMo desulfurization catalyst, a third bed: NiCoMo desulfurization catalyst A, and a fourth bed: NiCoMo desulfurization catalyst B. A desulfurization apparatus equipped with a catalyst layer having a floor structure was used.

Density of desulfurization raw material oil 1, ratio of catalytically decomposed heavy light oil c-1 in desulfurization raw material oil 1 (volume%), yield of desulfurized heavy light oil b-1 to desulfurization raw material oil 1 (volume%), thermal decomposition The yield (volume%) of the light oil content (Wild Product) obtained from the oil desulfurization apparatus (B) with respect to the desulfurization raw material oil 1, the hydrogen consumption (kNm ³ / day) in the thermal decomposition oil desulfurization apparatus (B), and heat. Table 3 shows the fuel (FOE-L / day) and the amount of electricity (KW / day) used in the cracked oil desulfurization apparatus (B).

(Step 3)
The desulfurized heavy oil distillate b-1 obtained in step 2, the direct desulfurized heavy oil distillate 1, and the desulfurized reduced pressure gas oil distillate 1 are combined with each other. Minute 1 = Approximately 30: Approximately 20: Approximately 50 (volume ratio), it is introduced into the fluid cracking apparatus (C) as a catalytic cracking raw material oil, and fluid cracking is performed at a reaction temperature of 515 ° C. Quality light oil c-1 and other distillates were obtained. The obtained catalytically cracked heavy gas oil c-1 was introduced into the above-mentioned pyrolysis oil desulfurization apparatus (B) and used in step 2. The characteristics of catalytically cracked heavy gas oil c-1 are also shown in Table 1.

[Comparative Example 1]
In Example 1, the catalytic cracking heavy oil (c) was not introduced into the thermal cracking desulfurization apparatus (B), but was introduced into the heavy oil thermal cracking apparatus (A) in the same manner as in Example 1. The heavy oil was treated. That is, the heavy oil was treated by each of the following steps.

(Step 1)
The vacuum distilled residue oil 1 derived from crude oil from the Middle East and the slurry oil discharged from the fluid cracking apparatus (C) are combined with the catalytically cracked heavy gas oil c-2 obtained in step 3 described later to be a pyrolyzed raw material oil. As No. 2, it was introduced into the heavy oil thermal cracking apparatus (A) and subjected to thermal cracking treatment at 500 ° C. and 0.1 MPaG (gauge pressure) to obtain cracked heavy oil crackers a-2 and other distillates. Table 1 shows the properties of the pyrolyzed heavy light oil a-2.

(Step 2)
The pyrolysis heavy gas oil a-2 obtained in step 1 is introduced into the pyrolysis oil desulfurization apparatus (B) as the desulfurization raw material oil 2, the reaction temperature is 350 ° C., the hydrogen partial pressure is 13.0 MPa, and the hydrogen / oil ratio. Hydrodesulfurization treatment was carried out under the conditions of 1,200 m ³ (normal) / m ³ and a liquid space velocity of 0.25 h ^-1 to obtain desulfurized heavy gas oil b-2 and other fractions. Table 2 shows the properties of desulfurized heavy gas oil b-2.

Density of desulfurization raw material oil 2, ratio of catalytically decomposed heavy light oil c-1 in desulfurization raw material oil 2 (volume%), yield of desulfurized heavy light oil b-2 to desulfurization raw material oil 2 (volume%), thermal decomposition The yield (volume%) of the light oil content (Wild Product) obtained from the oil desulfurization apparatus (B) with respect to the desulfurization raw material oil 2, the hydrogen consumption (kNm ³ / day) in the thermal decomposition oil desulfurization apparatus (B), and heat. Table 3 shows the fuel (FOE-L / day) and the amount of electricity (KW / day) used in the cracked oil desulfurization apparatus (B).

(Step 3)
The desulfurized heavy oil b-2 obtained in step 2, the direct desulfurized heavy oil distillate 1 and the desulfurized reduced pressure gas oil distillate 1 are combined with the desulfurized heavy oil b-2: direct desulfurized heavy oil distillate 1: desulfurized reduced pressure gas oil distillate 1. = Approximately 30: Approximately 20: Approximately 50 (volume ratio), introduced into the fluid cracking apparatus (C) as catalytic cracking raw material oil 2 to obtain catalytic cracking heavy gas oil c-2 and other distillates. It was. In the fluid cracking apparatus (C), the operating conditions (catalyst amount and reaction temperature) were adjusted to maintain the yield of light oil at the same level as in Example 1. The obtained catalytic cracking heavy gas oil c-2 was introduced into the above-mentioned heavy oil thermal cracking apparatus (A) and used in step 1.

<Economic effect>
Comparative Examples calculated from Example 1 and Comparative Example 1 in consideration of fluctuations in the planned sales price of products due to fluctuations in the yield of light oil and fluctuations in processing costs due to fluctuations in fuel consumption, electricity consumption and hydrogen consumption. The merit of heavy oil treatment in Example 1 based on 1 was 2,167 (thousand yen / day) as shown in Table 3. From this result, it was found that the productivity of the heavy oil treatment was improved in Example 1 as compared with Comparative Example 1, and a high economic effect was obtained.

From Table 3, in Example 1, the yield rate of the gas oil transferred from the heavy oil was higher than that in Comparative Example 1, and the kerosene distillate obtained as a product of the pyrolysis oil desulfurization apparatus (B) was increased. Was shown to be. Further, as described above, the heavy oil treatment in Example 1 had an economic effect (treatment merit) of 2,167 (thousand yen / day) as compared with Comparative Example 1.

Therefore, when looking at these processes as a whole, it is possible to economically increase the yield of light components from pyrolysis heavy diesel fuel without significantly increasing the operating cost, even though the operation is performed using existing equipment. It was found that it was possible and productivity was improved.

The method for treating heavy oil of the present invention can be effectively used in the field of petroleum refining.

A: Heavy oil pyrolysis device B: Thermal cracking oil desulfurization device C: Flow contact cracking device a: Thermal cracking heavy light oil b: Desulfurized heavy light oil c: Contact decomposition heavy light oil

Claims (5)

Step 1 of introducing heavy oil into the heavy oil thermal decomposition apparatus (A) and performing thermal decomposition to obtain a fraction (a) containing thermally decomposed heavy light oil.
Step 2 to obtain desulfurized heavy gas oil (b) by introducing the fraction (a) containing the pyrolysis heavy gas oil obtained in step 1 into the pyrolysis oil desulfurization apparatus (B) and performing hydrodesulfurization. When,
The step 3 of introducing at least a part of the desulfurized heavy light oil (b) obtained in the above step 2 into the fluid cracking apparatus (C) and performing catalytic cracking to obtain the catalytic cracking heavy oil (c). Have and
At least a part of the catalytically cracked heavy gas oil (c) obtained in the step 3 is introduced into the pyrolyzed oil desulfurization apparatus (B) together with the fraction (a) containing the pyrolyzed heavy gas oil, and the step. A method for treating heavy oil, which comprises performing 2. The method for treating heavy oil according to claim 1, wherein the raw material oil to be introduced into the fluidized catalytic cracking apparatus (C) contains desulfurized reduced pressure gas oil together with the desulfurized heavy oil (b). According to claim 1 or 2, the fraction (a) containing the pyrolyzed heavy light oil has a 30% distillation temperature of 400 to 430 ° C. and a 90% distillation temperature of 500 to 530 ° C. The method for treating heavy oil described. The catalytically cracked heavy light oil (c) introduced into the pyrolysis oil desulfurization apparatus (B) is characterized by having a 30% distillation temperature of 370 to 400 ° C. and a 90% distillation temperature of 410 to 440 ° C. The method for treating heavy oil according to any one of claims 1 to 3. The method for treating heavy oil according to any one of claims 1 to 4, wherein the hydrodesulfurization in the step 2 is carried out under the conditions of a reaction temperature of 250 to 450 ° C. and a hydrogen partial pressure of 3 to 20 MPa.

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