JP6258756B2 - Method for producing fuel oil base material - Google Patents

Description

  The present invention relates to a fuel oil base material obtained using a fluid catalytic cracking apparatus.

In the petroleum refining process, thermal cracking is a method for cracking hydrocarbon molecules at high temperatures without using a catalyst to obtain light hydrocarbons. In the field of oil refining, a number of pyrolysis processes have been proposed with increasing gasoline demand. However, because gasoline obtained by pyrolysis has a low octane number, gasoline production has been replaced by a catalytic cracking process.
Currently, pyrolysis is used as a method for obtaining basic chemical raw materials such as ethylene from naphtha. The heavy fraction mainly composed of C9 fraction obtained by fractionating pyrolyzed oil obtained by thermal decomposition of naphtha has a high density, and the distillation property obtained by distilling this heavy fraction has gasoline. The fraction corresponding to the base material is expected to have a very high octane number. Moreover, this heavy fraction can be classified into kerosene or light oil in the flash point and boiling range. Nevertheless, this heavy fraction has a characteristic odor, so it is difficult to use it as a fuel oil base material used for gasoline, kerosene, etc., and it was mainly used as boiler fuel.
On the other hand, in the method of cracking raw oil with a fluid catalytic cracking unit (hereinafter referred to as FCC unit), in order to increase the production of fuel oil, hydrocarbons such as by-products from waste plastics and petrochemical product manufacturing equipment A method of efficiently decomposing by supplying a polymer to an FCC apparatus has been proposed (see Patent Documents 1 and 2).
Thus, from the viewpoint of high added value, application of the above-described heavy fraction, which has been used as boiler fuel so far, to applications other than boiler fuel applications is also desired.

JP-A-10-310778 JP 2002-294251 A

  An object of this invention is to provide the fuel-oil base material obtained from the heavy fraction obtained by fractionating pyrolysis oil.

  The inventors used a heavy fraction obtained by fractionating a pyrolyzed oil obtained by thermal decomposition of naphtha as a raw material oil for a fluid catalytic cracker, and fractionating the obtained cracked oil to obtain a high fraction. The present inventors have found that a fuel oil base material such as a gasoline base material having a research octane number can be obtained, and based on this finding, the present invention has been completed.

That is, this invention provides the fuel oil base material shown below.
[1] Fuel obtained by fractionating cracked oil obtained by cracking raw oil containing heavy fraction obtained by fractionating pyrolyzed oil obtained by pyrolysis of naphtha using a fluid catalytic cracking device Oil base.
[2] The fuel oil base material according to [1], wherein the fuel oil base material is a gasoline base material having a research octane number of 91.5 or more.
[3] The fuel oil base material according to [1] or [2], wherein the density of the heavy fraction at 15 ° C. is 0.900 g / cm ³ or more.
[4] The fuel oil base material according to [1] or [2], wherein a sulfur content in the heavy fraction is 0.5% by mass or less.
[5] The fuel oil base material according to [4], wherein a sulfur content in the heavy fraction is 0.1% by mass or less.
[6] The 10 volume% distillation temperature by the distillation method based on ASTM D86 of the heavy fraction is 140 ° C. or higher and 190 ° C. or lower, and the 50 volume% distillation temperature is 150 ° C. or higher and 200 ° C. or lower. The fuel oil base material according to any one of [1] to [5].
[7] The raw material oil includes desulfurized oil processed by a desulfurization apparatus and the heavy fraction, and the heavy fraction is contained in an amount of 1% by volume to 10% by volume based on the total amount of the raw material oil. ] The fuel oil base material in any one of [6].
[8] The fuel oil base material according to any one of [1] to [7], wherein a distillation temperature of the heavy fraction is 100 ° C. or higher and 350 ° C. or lower.

  ADVANTAGE OF THE INVENTION According to this invention, the fuel oil base material obtained from the heavy fraction obtained by fractionating pyrolysis oil can be provided.

[Fuel oil base material]
The fuel oil base material according to the present embodiment uses a fluid catalytic cracking device (hereinafter referred to as an FCC device) to feed a raw material oil containing a heavy fraction obtained by fractionating a pyrolyzed oil obtained by naphtha pyrolysis. Fuel oil base materials such as gas fraction, PP fraction, BB fraction, FCC gasoline (FG) fraction, cracked light oil (LCO) fraction obtained by further fractionating the cracked oil obtained by cracking It is.
As one type of fuel oil base material according to the present embodiment, a heavy fraction obtained by fractionating pyrolysis oil is mixed with a predetermined amount of desulfurized heavy oil, for example, as FCC feedstock, and this is used as FCC feedstock. Examples include gasoline bases having a high research octane number obtained by fractionating the cracked oil obtained by fluid catalytic cracking with an apparatus.

The properties of each fuel oil base according to the present invention are preferably as follows.
<Gas content>
The total composition of C1 and C2 is preferably 40 mol% or more.
It is preferable that hydrogen is 20 mol% or less.
<PP fraction>
The composition of C3 is preferably 95 mol% or more.
<BB fraction>
The composition of C4 is preferably 95 mol% or more.
<FCC gasoline fraction (gasoline base material)>
It is preferable that the density at 15 ° C. is 0.7200 g / cm ³ or more. The sulfur content is preferably 70 ppm or less. The research octane number (RON) is preferably 91.5 or more. The higher the octane number, the better the anti-knock property. Therefore, the research octane number is more preferably 92.0 or more, and further preferably 93.0 or more.
<Decomposed light oil (LCO) fraction>
The density at 15 ° C. is preferably 0.9000 g / cm ³ or more. The sulfur content is preferably 0.30 wt% or less.
<Residual oil fraction>
The density at 15 ° C. is preferably 1.1000 g / cm ³ or less. The sulfur content is preferably 1.25 wt% or less.

The compositions of C1, C2, and hydrogen are values measured in accordance with JIS K 2301 “Fuel gas and natural gas—analysis and test method”.
The compositions of C3 and C4 are values measured in accordance with JIS K 2240 “Liquefied petroleum gas-composition analysis method”.
The density at 15 ° C. is a value measured according to JIS K 2249 “Determination method of density of crude oil and petroleum products and density / mass / capacity conversion table”.
The sulfur content is a value measured according to JIS K 2541 “Crude oil and petroleum products—Sulfur content test method”.
The research octane number is a value measured according to JIS K 2280.

[Method for producing fuel oil base]
Below, the raw material oil for obtaining the fuel oil base material which concerns on this embodiment, a manufacturing procedure, etc. are demonstrated.
<FCC feedstock>
The FCC raw material oil that can be used for producing the fuel oil base material will be described. As described above, the FCC raw material oil is obtained by mixing a predetermined amount of heavy fraction obtained by fractionating pyrolysis oil with desulfurized heavy oil. Examples of the desulfurized heavy oil that can be used as the FCC feedstock include indirect desulfurized heavy oil and direct desulfurized heavy oil.
(Heavy fraction obtained by fractionating pyrolysis oil)
In the present embodiment, the heavy fraction obtained by fractionating pyrolysis oil is, for example, a distillation temperature of 100 ° C. or higher among pyrolysis oil obtained by pyrolysis of naphtha such as an ethylene cracking furnace process. It refers to a fraction in the range of 350 ° C. or lower, preferably 140 ° C. or higher and 280 ° C. or lower.
The properties of the heavy fraction are as follows. The density of the heavy fraction at 15 ° C. is preferably 0.900 g / cm ³ or more, more preferably 0.93 g / cm ³ or more and 0.98 g / cm ³ or less. If the density of the heavy fraction at 15 ° C. is in the above range, the amount of coke deposited on the catalyst in the FCC apparatus can be reduced, and the load reduction and the reaction efficiency improvement of the catalyst regeneration facility can be achieved.
The sulfur content contained in the heavy fraction is 0.5% by mass or less, and preferably 0.1% by mass or less. When the sulfur content in the heavy fraction is 0.1% by mass or less, the load on the exhaust gas desulfurization facility and the gas recovery facility downstream of the FCC unit can be reduced.

The distillation properties of the heavy fraction in this embodiment are such that the 10 vol% distillation temperature (T10) by the distillation method based on ASTM D86 is 140 ° C. or higher and 190 ° C. or lower, and the 50 vol% distillation temperature (T50) is What is 150 degreeC or more and 200 degrees C or less is preferable. Moreover, what has 90 volume% distillation temperature (T90) of 170 degreeC or more and 260 degrees C or less is preferable.
If the distillation property of the heavy fraction is within the above range, the amount of coke deposited on the catalyst in the FCC apparatus can be reduced, and the load reduction and the reaction efficiency improvement of the catalyst regeneration facility can be achieved.
In the present embodiment, the density at 15 ° C. is a density measured by JIS K 2249 “Determination method of density of crude oil and petroleum products and density / mass / capacity conversion table”. The sulfur content is a value measured according to JIS K 2541 “Crude oil and petroleum products—sulfur content test method”. The research method octane number is a value obtained by a research method based on JIS K 2280.

  As the heavy fraction having the above properties, a heavy fraction containing a C9 fraction as a main component is preferably exemplified. Examples of the component contained in the C9 fraction include styrene, propylbenzene, methylethylbenzene, trimethylbenzene, indene, dicyclopentadiene, naphthalene and the like.

(Indirect desulfurization heavy oil)
As the FCC feedstock used in the production of the fuel oil base material according to the present embodiment, for example, heavy gas oil obtained by atmospheric distillation of crude oil, vacuum gas oil or the like is desulfurized with an indirect desulfurization apparatus (VH). The resulting desulfurized heavy gas oil (VHHGO), desulfurized vacuum gas oil (VHVGO), degassed oil obtained from a solvent degassing device, and the like can be used in combination.

(Direct desulfurized heavy oil)
As the FCC feedstock used in the production of the fuel oil base material according to this embodiment, the crude oil distillation residue (AR) and vacuum distillation residue (VR), heavy gas oil, catalytic cracking residue, screw Desulfurized heavy oil (DSAR) obtained by hydrodesulfurization and hydrocracking in a heavy oil direct desulfurization apparatus (RH) using a high-density petroleum fraction such as braking oil and bitumen can be used.
Hydrodesulfurization and hydrocracking to obtain desulfurized heavy oil (DSAR) is carried out in the presence of a catalyst, and the desulfurization rate required by optimizing reaction conditions such as reaction temperature, reaction pressure, and liquid space velocity And the degradation rate of heavy oil can be achieved.

The hydrodesulfurization and hydrocracking are usually carried out at a temperature of 300 to 450 ° C., preferably 330 to 420 ° C., more preferably 380 to 420 ° C. under a hydrogen pressure of usually 10 to 22 MPa, preferably 13 to 20 MPa. Is called. The liquid hourly space velocity (LHSV) is usually 0.1 to 10 ^-1, preferably 0.1~3h ^-1, a hydrogen / oil ratio is typically 200~10,000Nm ³ / KL, preferably 500～10,000Nm ³ / It is performed in the range of KL.

  The hydrodesulfurization and hydrocracking preferably include two steps, a hydrodemetallation treatment step as the first step and a hydrodesulfurization treatment step as the second step. Raw heavy oil is first hydrodemetallized in the hydrodemetallation process, which is the first step, and metal components such as vanadium and nickel that cause a decrease in the activity of the hydrodesulfurization catalyst are hydrogenated. Demetalized. Next, the distillate treated in the hydrodemetallation process is sent to the hydrodesulfurization process, which is the second process, and hydrodesulfurized. At this time, the first step and the second step can be performed in the same apparatus, but may be performed in different apparatuses. From the viewpoint of suppressing the deterioration of the catalyst, it is preferable that a separate metal removal device such as OCR is additionally provided upstream of the RH.

  As a specific means for realizing the function sharing between the first step and the second step, the pore structure of the catalyst support and the amount of supported metal are used as parameters. For example, in the first step, the pore size of the support is increased ( (Or reduce the amount of supported metal) to increase the pore volume of the catalyst and capture the large metal content of the molecule. In the second step, the surface area is large (the pore diameter is small and the number is large). Hydrodesulfurization of sulfur compounds is mainly performed using a catalyst that supports more active metal on the support. Each of these steps has the main function sharing as described above, but as a whole, hydrorefining treatment of raw material heavy oil is performed.

  As the catalyst used for hydrodesulfurization and hydrocracking, any known catalyst having hydrodemetallization ability and hydrodesulfurization ability can be used. For example, alumina, silica-alumina, zeolite or a mixture thereof, etc. A catalyst carrying a group V to VIII metal of the periodic table or a sulfide or oxide thereof can be used as the support. From the viewpoint of using an active metal suitable for hydrodesulfurization, nickel, cobalt, molybdenum, tungsten, or a combination thereof is preferably used as the metal of the Group V to VIII metal of the periodic table. In the present invention, since it is more excellent in hydrodesulfurization, hydrocracking and hydrogenation ability than heavy oil, a porous inorganic oxide carrier such as alumina is used as a catalyst for Co-Mo, Co-Mo- It is preferable to use a catalyst carrying a metal such as P, Ni—Mo, Ni—Mo—P or the like.

  As a reactor used in the above hydrodesulfurization and hydrocracking, a conventionally known type of reactor, for example, a fixed bed or a moving bed can be used, and any of a downflow type and an upflow type can be used. Good.

The reaction product obtained by hydrodesulfurization and hydrocracking in RH is separated into gas and liquid by a gas-liquid separator, and the liquid phase is separated by naphtha fraction, kerosene fraction, light oil fraction, It is fractionated into a desired fraction such as a heavy oil fraction and recovered. DSAR which is the heavy oil fraction obtained at this time is used as FCC feedstock.
In the above hydrodesulfurization and hydrocracking in RH, the desulfurization rate (HDS), denitrogenation rate (HDN), devanadium rate (HDV), denicking rate (HDNi), decarburized rate (HDCCR), desulfurization rate. The asphaltene ratio (HDAs) is preferably 80 to 90%, 35 to 40%, 75 to 80%, 65 to 75%, 50 to 55%, and 60% or more, respectively. These are all calculated as the removal ratio of each component from the amount of each component in the RH feedstock and product oil.
The obtained DSAR is preferably a heavy hydrocarbon hydrocarbon fraction having a boiling point of 330 ° C. or higher from the viewpoint that a fraction that can be a so-called middle fraction such as light oil is utilized as much as possible for light oil. The content of the component is preferably 70 to 90% by mass, and the content of the sulfur is preferably 0.2 to 0.5% by mass.

(Other FCC feedstock)
FCC equipment feedstocks include heavy fraction obtained by fractionating the above pyrolysis oil, indirect desulfurized heavy oil, direct desulfurized heavy oil, heavy light oil, reduced pressure as long as the effects of the present invention are not impaired. Light oil, degassed light oil, atmospheric residual oil and the like can be mixed and used.

<Composition of FCC feedstock>
The heavy fraction obtained by fractionating the above pyrolyzed oil can be used as an FCC feedstock without being mixed with other feedstock components. Moreover, the heavy fraction obtained by fractionating the above-mentioned pyrolysis oil can also be used by mixing with the indirect desulfurized heavy oil and direct desulfurized heavy oil described above. Further, it can be used by mixing with other FCC feedstocks described above.
When a heavy fraction obtained by fractionating the pyrolysis oil described above, an indirect desulfurized heavy oil, and a direct desulfurized heavy oil are mixed and used, the above-mentioned heavy fraction is more preferable from the viewpoint of yield improvement. From the viewpoint of improvement in yield and odor (odorless), it is preferable that the heavy fraction is contained in an amount of 1% by volume to 10% by volume based on the total amount of FCC feedstock, and more preferably 1% by volume to 5% by volume. It is as follows.
The indirect desulfurized heavy oil and the direct desulfurized heavy oil are preferably in a volume ratio of 50:50 to 95: 5 in order to maintain the heat balance of the FCC apparatus.

<FCC equipment>
In the method for producing a fuel oil base material according to the present embodiment, the FCC raw material oil described above is introduced into the FCC apparatus, and is subjected to catalytic cracking under the following processing conditions.
The heavy fraction obtained by fractionating the pyrolysis oil, the indirect desulfurized heavy oil and the direct desulfurized heavy oil are mixed in the pipe, and the mixed FCC feedstock is introduced into the FCC apparatus. The treatment conditions for catalytic cracking are preferably a reaction temperature of 480 ° C. or higher and 650 ° C. or lower, and more preferably a range of 480 ° C. or higher and 550 ° C. or lower.
The reaction pressure is preferably in the range of 0.02 MPa to 5 MPa, more preferably in the range of 0.2 MPa to 2 MPa.
The cracked oil obtained by the fluid catalytic cracking treatment is further divided into a gas fraction, a PP fraction (propane, propylene), a BB fraction (butane, butylene), and an FCC gasoline (FG) fraction (boiling point range 185 ° C.). Fraction), cracked light oil (LCO) fraction (boiling range 185 ° C. or more and 370 ° C. or less), and residue oil fraction (heavy circulating oil (HCO) + cracked residue (CLO)). Be retained. A fraction having a boiling range of 185 ° C. or higher and 210 ° C. or lower may be fractionated as an FG fraction depending on the operation policy.
When the reaction temperature and reaction pressure are within the above ranges, catalytic cracking occurs efficiently, and the yield (volume%) of the fuel oil base material obtained by fractionating the reaction product (cracked oil) obtained by catalytic cracking treatment Is increased.

The invention is explained in more detail with reference to examples. The present invention is not limited to these examples. In addition, the property and performance in each example were measured according to the following method.
[Evaluation method]
Each property was evaluated by the following method.
<Density at 15 ° C>
The density at 15 ° C. was measured in accordance with JIS K 2249 “Density test method and density / mass / capacity conversion table for crude oil and petroleum products”.
<Sulfur content>
The sulfur content was measured according to JIS K 2541 “Crude oil and petroleum products—Sulfur content test method”.
<Residual carbon content>
Residual carbon content was measured according to JIS K 2270 “Crude oil and petroleum products—residual carbon content test method”.
<Distillation properties>
Distillation of the heavy fraction of pyrolysis oil was measured according to ASTM D86. Indirect desulfurized heavy oil distillation was measured according to ASTM D6352. The direct desulfurized heavy oil distillation was measured according to ASTM D7169.
<Odor test>
This was done according to the three-point preference method. The case where there was no peculiar odor was A, the case where there was a little peculiar odor, B, and the case where it felt that there was a peculiar strong odor, C.

[Examples and Comparative Examples]
A heavy fraction having properties shown in Table 1 obtained by fractionating pyrolysis oil and desulfurized heavy oil having properties shown in Table 2 were introduced into a fluid catalytic cracking apparatus and processed. The treatment conditions in the fluid catalytic cracking apparatus were set to the following conditions and further fractionated to obtain a fuel oil base material. The yield of the obtained fuel oil base material, RON of FCC gasoline, and odor evaluation of the product are shown in Table 3.
The reaction conditions in the catalytic cracking apparatus were as follows.
Reaction temperature: 507 ° C
Reaction pressure: 0.23 MPa
Feedstock temperature: 240 ° C
Catalyst / oil = 8.9

[Evaluation results]
According to the embodiment, when a heavy fraction obtained by fractionating a pyrolysis oil obtained by pyrolysis of naphtha is used as a feedstock for an FCC unit, RON of the FCC gasoline fraction is improved. Was confirmed. In addition, if the blending ratio of the heavy fraction obtained by fractionating the pyrolysis oil used as the FCC feedstock is 1 vol% to 10 vol%, more preferably 1 vol% to 5 vol%, It is also preferable from the viewpoint of odor.

Claims (6)

Main component is C9 fraction obtained by fractionating pyrolyzed oil obtained by thermal decomposition of naphtha and having a density of 15 ° C. of 0.900 g / cm ³ or more and a distillation temperature of 100 ° C. or more and 350 ° C. or less. A fuel oil base material is obtained by fractionating a cracked oil obtained by cracking a raw oil containing a heavy fraction with a fluid catalytic cracking device at a reaction temperature of 480 ° C. to 650 ° C. and a reaction pressure of 0.02 MPa to 5 MPa. A method for producing a fuel oil base material to be obtained.   The method for producing a fuel oil base material according to claim 1, wherein the fuel oil base material is a gasoline base material having a research octane number of 91.5 or more.   The method for producing a fuel oil base according to claim 1 or 2, wherein a sulfur content in the heavy fraction is 0.5 mass% or less. The method for producing a fuel oil base material according to claim 3 , wherein a sulfur content in the heavy fraction is 0.1 mass% or less. The 10 vol% distillation temperature by distillation method in accordance with ASTM D86 of heavy fraction is at 140 ° C. or higher 190 ° C. or less, according to claim 1-4 50 vol% distillation temperature of 200 ° C. or less 0.99 ° C. or higher The manufacturing method of the fuel oil base material in any one of.   The said raw material oil contains the desulfurized oil processed with the desulfurization apparatus, and the said heavy fraction, The said heavy fraction is 1 volume% or more and 10 volume% or less on the basis of this raw material oil whole quantity. The manufacturing method of the fuel oil base material in any one.