JP5420826B2 - Method for producing ultra-low sulfur fuel oil - Google Patents

Description

The present invention, cracked gas oil which is distilled in a fluidized catalytic cracking of hydrocarbon oils (LCO: Light Cycle Oil) from about the preparation how to produce ultra low sulfur fuel oil.

Conventionally, fluid catalytic cracking (FCC) is performed in a refining process of crude oil. The main purpose of FCC is to produce gasoline and cracked light oil (LCO) from heavy oil. Since the LCO produced here contains a large amount of aromatic compounds, it does not satisfy the quality of light oil. Therefore, in general, it is used as a base material for A heavy oil or C heavy oil, or by mixing a small amount of LCO with another light oil base material.
However, there is a limit to the amount of LCO that can be mixed with other light oil bases, and due to the recent decline in demand for heavy oil, development of a technology that effectively utilizes LCO is expected.
For example, Patent Document 1 discloses a technique in which a distillate obtained by FCC is hydrogenated and used as light oil. The manufacturing method described in Patent Document 1 includes a first step to a third step, in which hydrodesulfurization of hydrocarbon oil is performed in the first step, and hydrogen sulfide and ammonia generated in the first step in the second step. In the third step, hydrodesulfurization is performed simultaneously with hydrogenation of the aromatic hydrocarbon.
Patent Document 2 discloses a method for reforming LCO into a high-octane aromatic gasoline base material.

JP 2001-107060 A JP-A-61-148295

However, Patent Document 1 has a problem that the hydrodesulfurization activity of the catalyst is reduced when a large amount of polycyclic aromatic compounds are present. There is also a problem that the hue of the light oil obtained is deteriorated. Furthermore, since aromatic hydrocarbons are completely hydrogenated, there is also a problem that the amount of hydrogen consumption is large. As a method for preventing these problems, hydrodesulfurization may be considered at a low temperature. However, since the process includes the second step of separating a gas having a high hydrogen sulfide concentration, the process becomes complicated and is not practical. . Furthermore, an expensive noble metal catalyst must be used to increase the hydrogenation activity of the aromatic hydrocarbon, which is not economically effective.
In Patent Document 2, the LCO is hydrogenated and then passed again to the FCC unit. However, not only is the hydrogenated naphthene decomposed, but the hydrogen transfer reaction by the naphthene fraction occurs together with the olefin content. Decreases. Therefore, there exists a problem that the octane number of the refined gasoline fraction falls.

Therefore, an object of the present invention is to produce an ultra-low sulfur fuel oil useful as a light oil base or a gasoline base from cracked light oil (LCO: Light Cycle Oil) distilled by fluid catalytic cracking of hydrocarbon oil. it is to provide a manufacturing how sulfur fuel oil.

The method for producing an ultra-low sulfur fuel oil according to the present invention is the production of an ultra-low sulfur fuel oil that produces ultra-low sulfur fuel oil from cracked light oil (LCO: Light Cycle Oil) distilled by fluid catalytic cracking of hydrocarbon oil. In the method, the LCO is divided into a light cracked gas oil fraction having a ratio of monocyclic aromatic components of 0.5 to 1.0 with respect to the total aromatic components, and bicyclic and tricyclic aromatic components. A heavy cracking gas oil fraction having a ratio of 0.5 to 1.0 with respect to the total aromatic content, and a fractionation temperature of the light cracked gas oil fraction being set in a range of 200 ° C. to 290 ° C. A first desulfurization step of producing a first light oil base material by mixing a straight-run gas oil with the light cracked gas oil fraction distilled in the separation step and performing hydrodesulfurization treatment And desulfurizing the heavy cracked light oil fraction separated in the separation step to produce a desulfurized heavy cracked light oil. Degree and, which comprises carrying out the, the decomposition process of manufacturing with the desulfurized heavy cracked gas oil decompose to gasoline base material and the second gas oil bases.

The ultra-low sulfur fuel oil produced in the present invention is a gasoline base and a light oil base.
Fluid catalytic cracking is usually done by fluid catalytic cracking (FCC) using heavy gas oil (HGO) or vacuum gas oil (VGO) as raw material, and residual oil fluid catalytic cracking using raw material that contains a lot of asphaltenes. Although it may be distinguished from (RFCC: Residue fluid catalytic cracking), the fluid catalytic cracking of the present invention includes both FCC and RFCC, and the LCO distilled in any process is also the object of the present invention.
Hereinafter, the light cracked light oil fraction may be referred to as an LLCO fraction, and the heavy cracked light oil fraction may be referred to as an HLCO fraction.

According to this invention, LCO is separated into an LLCO fraction with a high ratio of monocyclic aromatics and an HLCO fraction with a high ratio of bicyclic and tricyclic aromatics, and a desulfurization step is performed on the LLCO fraction. The HLCO fraction is further subjected to a desulfurization step and then a decomposition step.
Since LCO contains a large amount of aromatics, the sulfur content is not reduced sufficiently even if desulfurization is performed by a conventional hydrodesulfurization treatment. Therefore, an ultra-low sulfur gas oil base and gasoline base can be efficiently and economically produced without wastefully consuming hydrogen in the desulfurization step.

Specifically, in the light cracked light oil (LLCO) fraction, the ratio of the monocyclic aromatic component is 0.5 or more and 1.0 or less with respect to the total aromatic component, preferably 0.6 to 0.8. is there. When the ratio of the monocyclic aromatic component is less than 0.5, it is not preferable because the effect on the competitive adsorption poisoning of the polycyclic aromatic hydrodesulfurization reaction and further on the catalyst deterioration is increased. On the other hand, if it exceeds 0.8, for example, when the LLCO fraction from the LCO is separated by distillation, the yield of the LLCO fraction becomes too small, which is not efficient.
The heavy cracked light oil (HLCO) fraction has a ratio of bicyclic and tricyclic aromatics of 0.5 to 1.0, preferably 0.6 to 0.8, based on the total aromatics. It is. If the ratio of the 2-ring and 3-ring aromatics is less than 0.5, since there are many 1-ring aromatics, it is sufficient to simply carry out the dealkylation reaction, and there is no need to apply a hydrocracking treatment. The upper limit may be 1.0 or less, but the amount of hydrogen consumed for hydrogenation of tricyclic aromatics is large, and there is a risk of sudden heat generation in the catalyst layer. The following is preferable.

A light oil base produced by such a production method has properties of a sulfur content of 10 ppm or less and a cetane index of 50 or more, and thus is useful as a normal light oil.
Moreover, since the gasoline base material manufactured by desulfurization and decomposition | disassembly of an HLCO fraction has the property that a sulfur content is 10 ppm or less and an octane number is 80 or more, it can be used as a normal gasoline base material. Moreover, this gasoline base material contains many aromatic components having 6 to 8 carbon atoms. Examples of the aromatic component having 6 to 8 carbon atoms include benzene, toluene, xylene (BTX) and the like, and particularly, a large amount of xylene is contained. Therefore, an aromatic component having 6 to 8 carbon atoms can be effectively used as a petrochemical raw material.
Furthermore, since the second light oil base material obtained simultaneously with the gasoline base material by decomposition of the HLCO fraction has a sulfur content of 10 ppm or less, this can also be used effectively.
Thus, ultra-low sulfur and useful light oil base and gasoline base can be produced from LCO.
Further, according to the production method of the present invention, it is possible to produce many desired fuel oils among the above ultra-low sulfur fuel oils by slightly changing the LCO fractionation conditions and the desulfurization HLCO fraction decomposition conditions. Therefore, the fuel oil corresponding to the demand at that time can be selected and manufactured, so that it can be carried out efficiently without waste.

In the method for producing ultra-low sulfur fuel oil of the present invention, the separation step, carried out in the range of 200 ° C. or higher 290 ° C. or less distillation temperature of the LLCO fraction.
For example, this separation step can be carried out in a distillation column.
The compositions of the 1-3 ring aromatic components differ depending on the distillation temperature. Therefore, a fraction containing a large amount of the desired aromatic component can be obtained by changing the distillation temperature. That is, a light cracked light oil (LLCO) fraction containing a large amount of monocyclic aromatic components and a heavy cracked light oil (HLCO) fraction containing a large amount of bicyclic and tricyclic aromatic components can be easily fractionated. .

In this invention, since distillation is performed in the range of 200 ° C. or more and 290 ° C. or less, fractionation is performed into an LLCO fraction containing a large amount of monocyclic aromatic components and an HLCO fraction containing a large amount of bicyclic and tricyclic aromatic components. Can do. A more preferable temperature range is 230 ° C. or higher and 270 ° C. or lower.
When the fractional distillation point is less than 200 ° C., for example, when the LLCO fraction is separated from LCO by distillation, the yield of the LLCO fraction becomes too small, which is not efficient. Moreover, when it exceeds 290 degreeC, since the influence which it has on competitive adsorption poisoning to the hydrodesulfurization reaction of a polycyclic aromatic, and also catalyst deterioration becomes large, it is unpreferable.

In the method for producing ultra-low sulfur fuel oil of the present invention, the first desulfurization step, you implement hydrodesulfurization process by mixing the straight run gas oil with said light cracked gas oil fraction.
Moreover, it is preferable to implement the mixing ratio of the straight-run gas oil as 40 to 80% by volume.
According to the present invention, the hydrodesulfurization treatment is carried out by mixing straight-run gas oil in the range of 40 to 80% by volume with the LLCO fraction having a large amount of monocyclic aromatics. It can be 50 or more. A cetane index of 50 or more is effective as a normal light oil base.
A more preferable mixing ratio of straight-run gas oil is 50 to 80% by volume. When the mixing ratio of straight-run gas oil is less than 40% by volume, it is difficult to set the cetane index to 50 or more. Moreover, it is not economical to exceed 80 volume%.

In the method for producing an ultra-low sulfur fuel oil of the present invention, the first desulfurization step is performed at a hydrogen partial pressure of 2 MPa to 10 MPa, and at least any one of Group 6, 8, 9, and 10 metals in the periodic table. It is preferable to carry out the hydrodesulfurization treatment using a hydrodesulfurization catalyst containing one of these.
In this invention, since a catalyst containing at least one of Group 6, 8, 9, and 10 metals of the periodic table is used, desulfurization can be performed efficiently, and the sulfur content is 10 ppm or less. A sulfur light oil base material can be produced.

And in the manufacturing method of the ultra-low-sulfur fuel oil of the present invention, the second desulfurization step is performed at a hydrogen partial pressure of 5 MPa or more and 15 MPa or less, and among periodic group sixth, eighth, ninth and tenth metals. It is preferable to carry out the hydrodesulfurization treatment using a hydrodesulfurization catalyst containing at least one of them.
In the present invention, since a catalyst containing at least one of Group 6, 8, 9, and 10 metals of the periodic table is used, desulfurization can be efficiently performed and desulfurized heavy having a sulfur content of 10 ppm or less. It can be a pyrolysis light oil (HLCO) fraction.

Furthermore, in the method for producing an ultra-low sulfur fuel oil according to the present invention, the cracking step comprises hydrogenation using a hydrocracking catalyst containing Group 6 and Group 8 metals of the periodic table and further containing crystalline aluminosilicate. It is preferable to carry out a chemical decomposition treatment.
In the present invention, the treatment of the HLCO fraction consists of two stages, a second desulfurization process and a decomposition process. The HLCO fraction is desulfurized by hydrodesulfurization treatment in the second desulfurization step, and is decomposed into an ultra-low sulfur gasoline base and light oil base by hydrocracking in the cracking step.
In the second desulfurization step, the hydrodesulfurization catalyst containing at least one of the metals in Groups 6, 8, 9, and 10 of the periodic table is used, so that the HLCO fraction can be efficiently desulfurized. it can. Also, in the desulfurization step of the desulfurized HLCO fraction, hydrocracking is performed using a hydrocracking catalyst containing Group 6 and Group 8 metals of the periodic table, so that it is decomposed into a gasoline base and a light oil base. Can do.
As described above, since the HLCO fraction is desulfurized in the second desulfurization step and then decomposed in the second decomposition step, the HLCO fraction can be effectively decomposed. Therefore, it is possible to produce a gasoline base material having a sulfur content of 10 ppm or less and an octane number of 80 or more and an aromatic content of 6 to 8 carbon atoms and a diesel oil base material having a sulfur content of 10 ppm or less.

In the method for producing an ultra-low sulfur fuel oil of the present invention, it is preferable that the crystalline aluminosilicate is a Y-type zeolite and contains iron. Furthermore, the hydrocracking catalyst preferably contains the crystalline aluminosilicate in an amount of 10% by mass to 80% by mass.
By these inventions, the HLCO fraction can be effectively decomposed into a gasoline base containing a very low sulfur, a high octane number, and a large amount of aromatics having 6 to 8 carbon atoms, and a super low sulfur light oil base. it can.

Hereinafter, an embodiment of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic view showing an aspect of a production apparatus for producing a low sulfur fuel oil from cracked light oil (LCO) according to the present embodiment. As shown in FIG. 1, the manufacturing apparatus 100 includes a separation apparatus 10 that separates an LCO distilled from a fluid catalytic cracking (FCC) apparatus into a light cracked light oil (LLCO) fraction and a heavy cracked light oil (HLCO); The first hydrodesulfurization apparatus 20 for hydrodesulfurizing the LLCO fraction, the second hydrodesulfurization apparatus 30 for hydrodesulfurizing the HLCO fraction, and hydrocracking the desulfurized desulfurized HLCO fraction Hydrocracking device 40.
In the present embodiment, the separation process is performed by the separation apparatus 10, the desulfurization process is performed by the hydrodesulfurization apparatuses 20 and 30, and the decomposition process is performed by the hydrocracking apparatus 40. Each step will be described in detail below.

[1. Separation process]
The separation step is a step of separating the LCO into an LLCO fraction and an HCLO fraction, and is performed by the separation device 10. The separation device 10 is connected to an FCC device and includes a fractionation tower 101.
The FCC apparatus normally produces gasoline and LCO from heavy oil, but the product contains a large amount of aromatics and olefins. Particularly preferred as the feedstock oil for the FCC unit is heavy gas oil, vacuum gas oil, atmospheric residual oil, degassed oil, crude oil and those obtained by desulfurizing them in advance, and mixtures thereof.
The LCO produced in the FCC apparatus is introduced into the separation apparatus 10 and distilled in the fractionation tower 101. The LLCO fraction is fractionated from the top of the fractionation tower 101 and the HLCO fraction is separated from the bottom of the tower.
Here, the LLCO fraction is a fraction in which the ratio of the monocyclic aromatic compound is 0.5 or more and 1.0 or less among the total aromatic compounds contained in the LLCO fraction. Further, the HLCO fraction is a fraction in which the ratio of aromatic compounds having two or more rings among the total aromatic compounds contained in the HLCO fraction is 0.5 or more and 1.0 or less.

When the content of the aromatic compound of LCO as a raw material was analyzed by high performance liquid chromatography, the result shown in FIG. 2 was obtained. As can be seen from FIG. 2, the lower the fractionation temperature, the more dicyclic aromatic compounds are distilled, and the higher the fractionation temperature, the more dicyclic and tricyclic polycyclic aromatic compounds are distilled. In order to separate the LLCO fraction containing a large amount of monocyclic aromatic compounds into the HLCO fraction containing a large amount of aromatic compounds containing two or more rings, the fractionation temperature of the LLCO fraction is in the range of 200 ° C. or higher and 290 ° C. or lower. It is preferable to do.
Further, in order to obtain a target fraction, an optimum temperature can be appropriately selected within this temperature range. For example, when it is desired to fractionate more LLCO fractions, for example, the fractionation temperature may be set within a range of 240 ° C. or higher and 290 ° C. or lower. Moreover, what is necessary is just to set the fraction temperature in the range of 200 degreeC or more and 240 degrees C or less when it wants to isolate | separate many HLCO fractions. In this way, the fractionation temperature can be adjusted according to the target fraction ratio.

[2. First desulfurization process]
Among the fractions separated in the separation step, the LLCO fraction is passed through the first hydrodesulfurization apparatus 20 and desulfurized to a sulfur content of 10 ppm or less. This step is the first desulfurization step.
The first hydrodesulfurization device 20, the reaction temperature 320 ° C. or higher 400 ° C. or less, or less hydrogen partial pressure 2MPa least 10 MPa, liquid hourly space velocity (LHSV) 0.3h ^-1 or 2.0 h ^-1 or less, operated at conditions Is done. Moreover, what carried | supported at least 1 sort (s) in the periodic table 6th, 8th, 9th, 10th metal on the refractory oxide support | carrier can be used as a hydrodesulfurization catalyst. Examples of the refractory oxide carrier include alumina, silica, silica alumina, titania, magnesia, zinc oxide, crystalline aluminosilicate, clay mineral, or a mixture thereof. Among these, alumina, particularly γ-alumina is preferable. The average pores are preferably in the range of 50 to 150 mm, more preferably in the range of 60 to 140 mm. The shape may be a powder or a molded body such as a cylinder, a three-leaf, or a four-leaf.

The LLCO fraction of LCO is mixed with straight-run gas oil and passed through the hydrodesulfurization apparatus 20. By mixing with straight run diesel oil, the cetane index of the diesel oil produced can be improved.
From the above, the LLCO fraction can produce a light oil base material having a sulfur content of 10 ppm or less and a cetane index of 50 or more through such a desulfurization step.

[3. Second desulfurization process]
Among the fractions separated in the separation step, the HLCO fraction is passed through the second hydrodesulfurization apparatus 30 and desulfurized. This step is the second desulfurization step.
The second hydrodesulfurization apparatus 30 can use the same hydrodesulfurization catalyst as that used in the first hydrodesulfurization apparatus 20, and thereby desulfurize the HLCO fraction.

Second hydrodesulfurization device 30, the reaction temperature 320 ° C. or higher 430 ° C. or less, or less hydrogen partial pressure 5MPa above 15 MPa, operating at a liquid hourly space velocity (LHSV) 0.3h ^-1 or 2.0 h ^-1 or less, the conditions Is done. Under such conditions, a desulfurized HLCO fraction having a sulfur content of 10 ppm or less can be obtained.

[4. Decomposition process]
The desulfurized HLCO hydrodesulfurized in the second desulfurization step is passed through the hydrocracking apparatus 40 and hydrocracked. This process is a decomposition process.
Hydrocracker 40, the reaction temperature 320 ° C. or higher 430 ° C. or less, or less hydrogen partial pressure 5MPa above 15 MPa, liquid hourly space velocity (LHSV) 0.3h ^-1 or 2.0 h ^-1 or less, operated at conditions. Under such conditions, a decomposition rate of the HLCO fraction in the range of 30% by mass or more and 90% by mass or less can be obtained.
Further, a hydrocracking catalyst containing crystalline aluminosilicate can be used as the catalyst. As the hydrocracking catalyst, a catalyst in which at least one of the metals in Groups 6, 8, 9, and 10 of the periodic table is supported on a refractory oxide carrier can be used. Examples of the refractory oxide carrier include those containing alumina, silica / alumina, silica, or crystalline aluminosilicate. The content of the crystalline aluminosilicate in the refractory oxide carrier is preferably 10% by mass or more and 80% by mass or less, but 50% by mass or more and 80% by mass or less from the viewpoint of exhibiting high hydrocracking activity. More preferably.

Furthermore, examples of the crystalline aluminosilicate include Y-type zeolite, β zeolite, and mordenite. In particular, those obtained by modifying or stabilizing Y-type zeolite are preferred.
As a modification method of Y-type zeolite, there is a method of ion exchange with iron ions. The physical properties of the Y-type zeolite iron ion _{exchange, Si0 2 / Al 2 O 3} ( molar ratio) is 3.5 or more, preferably 4.6 or more. Further, those having a lattice constant of 24.20 to 24.40 are preferred.
Moreover, as a stabilization process of a Y-type zeolite, the method of implementing a steaming process under water vapor | steam within the range of 540 degreeC or more and 810 degrees C or less is mentioned. Mineral acid is added to the crystalline aluminosilicate after the steaming treatment to clean the dealuminated aluminum and fallen aluminum. In the case of further modification with iron, it is preferable to add iron sulfate and mix and agitate to carry the iron supported and the dealumination and removal of the dropped aluminum.

[4. Method for producing ultra-low sulfur fuel oil]
Next, a specific method for producing an ultra-low sulfur fuel oil will be described.
First, the LCO obtained by the FCC device is passed through the separation device 10. LCO is distilled at a fractionation tower 101 of the separation apparatus 10 at a temperature in the range of 200 to 290 ° C., for example, 240 ° C. A fraction fractionated from the top of fractionator 101 is defined as an LLCO fraction, and a fraction remaining at the bottom of the column is defined as a first HLCO fraction.
The LLCO fraction is passed through the first hydrodesulfurization unit 20 together with the straight-run gas oil fraction and desulfurized to become a light oil base material having a sulfur content of 10 ppm or less and a cetane index of 50 or more.
On the other hand, the HLCO fraction is passed through the second hydrodesulfurization apparatus 30 and desulfurized. The desulfurized HLCO fraction is then passed through the hydrocracking apparatus 40 for cracking. And after a distillation step (not shown), a sulfur content of 10 ppm or less, a research octane number (RON: Research Octane number) of 80 or more, and a gasoline base containing a large amount of aromatics having 6 to 8 carbon atoms and a sulfur content of 10 ppm or less Can be produced. At this time, the gasoline base is produced at a rate of 50% by volume or more, and the light oil base is produced at a rate of 20% by volume or less.

[5. Effects of this embodiment]
According to this embodiment, the LCO fraction obtained by the FCC apparatus is separated into an LLCO fraction and an HLCO fraction, and the sulfur content is 10 ppm or less by desulfurizing the LLCO fraction by the first hydrodesulfurization treatment. Can be produced. Moreover, since the straight gas oil fraction is mixed in the desulfurization step, the obtained light oil base material has a high cetane index of 50 or more, and is useful as a normal light oil base material. In addition, since the LLCO fraction obtained in the separation step has properties as kerosene, it can be used as a kerosene base material.

Further, the second hydrodesulfurization treatment and the hydrocracking treatment of the HLCO fraction can be performed to produce an ultra-low sulfur gasoline base material and an ultra-low sulfur light oil base material. Since the gasoline base has a research octane number of 80 or more, it is useful as a normal gasoline base and further contains 10 mass% or more of aromatics having 6 to 8 carbon atoms. Can also be used.
Since the light oil base material and gasoline base material obtained in the present embodiment all have a low sulfur content of 10 ppm or less, it is possible to provide a fuel oil that is environmentally friendly and meets environmental regulations. Moreover, since the property as a light oil base material or a gasoline base material is also provided, it can utilize effectively.

In the present embodiment, the fractionation temperature can be adjusted in the range of 200 ° C. or more and 290 ° C. or less in accordance with the ratio of the desired LLCO fraction and HLCO fraction in the separation step. The ratio of the light oil base and the gasoline base can be adjusted. That is, many desired fuel oils can be manufactured only by changing fractional distillation temperature.
In addition, the aromatic component having 6 to 8 carbon atoms of the gasoline base material finally obtained is a bicyclic or tricyclic aromatic component contained in the HLCO fraction which is a raw material oil in the second hydrodesulfurization treatment step and the decomposition step. The more groups there are, the more they are produced. Therefore, the content of aromatics having 6 to 8 carbon atoms can be adjusted by changing the composition of the HLCO fraction. That is, a large amount of fuel oil corresponding to the demand at that time can be produced by a simple operation of adjusting the fractionation temperature in the fractionation tower 101.

[6. Modification of this embodiment]
It should be noted that the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.
For example, in the above-described embodiment, the LCO fraction obtained from the FCC device is passed through the separation device 10 and separated into the LLCO fraction and the HLCO fraction. However, the LCO fraction obtained from the RFCC device is separated. Oil may be passed through the device 10.

  In the above embodiment, straight-run gas oil is mixed with the LLCO fraction in the first desulfurization step. However, this is not limited to straight-run gas oil. For example, hydrodesulfurized gas oil (DGO) may be used. Good. When DGO is used, it is preferably mixed after the desulfurization step of the LLCO fraction.

EXAMPLES Next, although an Example is given and this invention is demonstrated in more detail, this invention is not restrict | limited at all to the content of description of these Examples.
After performing a bench test of the separation step in this embodiment (Test 1), a hydrodesulfurization treatment bench test in the desulfurization step in this embodiment (Test 2), and a hydrocracking treatment bench test in the decomposition step in this embodiment (Test 3) was performed.

<Test 1>
The cracked light oil (LCO) fraction obtained from the FCC unit is separated into a light cracked light oil (LLCO) fraction and a heavy cracked light oil (HLCO) fraction by a distillation device, and the obtained LLCO fraction and HLCO fraction are separated. The properties of the minutes were analyzed.
For the sulfur content, the radiative excitation method (JIS K2541-4 “Crude oil and petroleum products-Sulfur content test method Part 4: Radiation excitation method”) is used, and for the density, the vibration density method (JIS K2249 “crude oil and petroleum products”). Product-density test method (vibration density test method) "), nitrogen content is chemiluminescence method (JIS K2609" crude oil and petroleum products-nitrogen content test method (chemiluminescence method) "), saturated hydrocarbon content, olefin For the composition of components such as water and aromatics, the high performance liquid chromatogram method (JPI-5S-49-97 “Petroleum products—hydrocarbon type test method—high performance liquid chromatographic method”) was used. Moreover, the cetane index was calculated | required from the measured value using the cetane index calculation method (JIS K2280 "petroleum product-fuel oil-octane number and a cetane number test method and a cetane index calculation method").

[Example 1]
With the distillation end point (EP) of the LLCO fraction as the target of the fractionation temperature, fractionation was performed at a fractionation temperature of 230 ° C. so that the ratio of the LLCO fraction to the HLCO fraction was 20/80 mass%.

[Example 2]
The fractionation was performed at a fractionation temperature of 270 ° C. so that the ratio of the LLCO fraction and the HLCO fraction was 40/60% by mass.

[Comparative Example 1]
In order to compare with Example 1 and Example 2, the property of the LCO fraction before separation was analyzed.
The analysis results of the samples of Examples 1 and 2 and Comparative Example 1 are shown in Table 1 below.

  As can be seen from Table 1, the LLCO fractions of Example 1 and Example 2 have a high ratio of 1-ring aromatics in the total aromatics, and the HLCO fraction is a 2-ring + 3-ring aroma in the total aromatics. High proportion of tribes. Thus, the ratio of the LLCO fraction and the HLCO fraction can be adjusted.

<Test 2>
Hydrodesulfurization treatment was performed using the LLCO fraction obtained in Test 1.
In the hydrodesulfurization treatment, the samples shown in Examples 3 and 4 and Comparative Example 2 were passed through reaction tubes filled with 100 cc of the hydrodesulfurization catalyst shown below, and the properties of the samples after passing through were analyzed and evaluated. did.
The hydrodesulfurization catalyst used in the hydrodesulfurization treatment was prepared by impregnating and supporting a metal solution containing nickel, molybdenum and phosphorus on a support obtained by impregnating and supporting an aqueous titanium solution on an alumina support. Details are as follows.

95 g of basic nickel carbonate (FLUKA: NiO ₂ ; 62.3 mass%), 323 g of molybdenum trioxide and 39 g of normal phosphoric acid (purity 80 mass%) are added to 1000 cc of ion-exchanged water and dissolved at 80 ° C. with stirring. After concentration at 80 ° C., the mixture was cooled to room temperature and adjusted to 500 cc with pure water to prepare a nickel molybdenum phosphorus impregnating solution (S1).

500 g of titanium tetrachloride and 1 liter of pure water were each cooled in an ice water cooling bath. The cooled pure water was stirred, and titanium tetrachloride was gradually added dropwise while cooling to obtain a colorless titania sol hydrochloric acid solution. To this titania sol solution, 1.2 times equivalent of ammonia water (concentration: 1 mol / l) was added dropwise and stirred for 1 hour to obtain a titanium hydroxide gel. The gel was separated by suction filtration, redispersed in about 1 liter of pure water, and washed by filtration. This operation was repeated 4 to 5 times until the washing solution became neutral to remove the chlorine radicals.
11 g of the resulting titanium hydroxide gel was collected as TiO ₂ . 50 cc of 25% by mass ammonia water was added thereto and stirred. Furthermore, 100 cc of 30% by mass hydrogen peroxide solution was gradually added to dissolve the titania gel to obtain a peroxotitanium solution. Thereto, 29 g of citric acid monohydrate was gradually added, the temperature was slowly raised while stirring, and excess hydrogen peroxide solution was removed at 50 ° C. Furthermore, the solution was concentrated at 80 ° C. until the total amount became 117 cc, and a yellow-orange transparent hydroxycarboxylatotitanium ammonium liquid (T1) was obtained.

  To 100 g of γ-alumina carrier (A1) having a water absorption rate of 0.8 cc / g, 60 cc of hydroxycarboxylatotitanium ammonium solution (T1) was diluted with pure water so as to match the amount of water absorption, and impregnated at normal pressure. After drying in vacuum at 1 ° C. for 1 hour, drying in a dryer at 120 ° C. for 3 hours and firing at 500 ° C. for 4 hours gave a carrier (A2).

  50 cc of nickel-molybdenum phosphorus impregnation liquid (S1) was sampled, 6 g of triethylene glycol was added, and 100 g of carrier (A2) having a water absorption rate of 0.75 cc / g was adjusted with pure water to match the water absorption rate. The solution was impregnated under normal pressure and dried at 120 ° C. for 16 hours to prepare a hydrodesulfurization catalyst.

[Reference Example 1]
As a reference example, only straight-run gas oil from general Middle Eastern crude oil was passed through the reaction tube.

[Example 3]
20% of the LLCO fraction of Example 1 was mixed with the straight-run gas oil of Reference Example 1.

[Example 4]
20% of the LLCO fraction of Example 2 was mixed with the straight-run gas oil of Reference Example 1.

[Comparative Example 2]
The straight-run gas oil of Reference Example 1 was mixed with 15% of LCO of Comparative Example 1.

[Comparative Example 3]
The straight-run gas oil of Reference Example 1 was mixed with 20% of LCO of Comparative Example 1.
Table 2 below shows the properties of the samples of Examples 3 and 4 and Comparative Examples 2 and 3 before and after the hydrodesulfurization treatment. In addition, WAT (Weight Average Temperature) in Table 2 is a temperature at which the sulfur content in the produced oil is achieved.

As can be seen from Comparative Example 2 and Comparative Example 3 in Table 2, in order to maintain a cetane index of 55 or more after hydrodesulfurization treatment of the LCO fraction, the mixing ratio of the LCO fraction is increased only to 15%. I can't. Moreover, WAT for obtaining a sulfur content of 8 ppm increased by 7 ° C. compared to the reference example.
On the other hand, since Example 3 and Example 4 are LLCO fractions containing a large amount of monocyclic aromatics, even when the mixing ratio was increased to 20%, a good value of cetane index 57 was obtained. Moreover, WAT for obtaining a sulfur content of 8 ppm is almost the same as that of the reference example.
Therefore, it can be seen that the LLCO fraction having a high ratio of monocyclic aromatics can be mixed with straight-run gas oil at a high ratio, and an ultra-low sulfur gas oil base material having a high cetane index can be produced.

<Test 3>
Hydrodesulfurization treatment and hydrocracking treatment were performed using the HLCO fraction obtained in Test 1.
The hydrodesulfurization treatment and the hydrocracking treatment were carried out in the same manner as in Examples 5 and 6 in reaction tubes filled with the hydrodesulfurization catalyst used in Test 2 and the hydrocracking catalyst shown below at a ratio of 50/50 vol% The samples shown in Comparative Examples 4 to 6 were passed through, and the aromatic components having 6 to 8 carbon atoms contained in the samples after passing through were evaluated.
The hydrocracking catalyst used in the hydrocracking treatment was prepared by impregnating and supporting a metal solution containing nickel / molybdenum on an alumina carrier as follows.

Synthetic Na—Y zeolite (Na ₂ O content: 13.3 mass%, SiO ₂ / Al ₂ O ₃ molar ratio: 5.0) was subjected to ammonium ion exchange, and NH ₄ —Y zeolite Na ₂ O content: 1. 3% by mass) was obtained. This was steamed at 580 ° C. to obtain a steamed zeolite. After 10 kg of steamed zeolite was suspended in 115 liters of pure water, the suspension was heated to 75 ° C. and stirred for 30 minutes. Next, 63.7 kg of 10 mass% sulfuric acid solution was added to this suspension over 35 minutes, and 11.5 kg of ferric sulfate solution having a concentration of 0.57 mol / l was added over 10 minutes. After stirring, filtration and washing were performed to obtain an iron-containing crystalline aluminosilicate slurry I having a solid content concentration of 30.5% by mass. A portion of this iron-containing crystalline aluminosilicate slurry I was taken and dried, and then the pore structure was measured.
As the pore structure, the pore volume of 600 Å or less is 0.5393 cc / g, the proportion of the pore volume of 50 to 300 に in the pore volume of 600 Å or less is 22.8%, and the pore volume of 100 to 300 Å The volume percentage was 15.6%.

Next, the alumina slurry was adjusted. 80 kg of sodium aluminate solution (concentration of Al ₂ O ₃ : 5.0% by mass) and 240 g of 50% by mass of gluconic acid solution were placed in a stainless steel container with a steam jacket having an internal volume of 200 liters and heated to 60 ° C. Next, 88 kg of aluminum sulfate solution (Al ₂ O ₃ equivalent concentration: 2.5 mass%) is prepared in a separate container, this diluted aluminum sulfate solution is added so that the pH becomes 7.2 in 15 minutes, and an aluminum hydroxide slurry ( Preparation slurry I) was obtained.

The blended slurry I was further aged for 60 minutes while maintaining the temperature at 60 ° C. Next, the total amount of the prepared slurry was dehydrated with a flat plate filter and washed with 600 liters of 0.3% by mass ammonia water at 60 ° C. to obtain an alumina cake. A part of this alumina cake was used pure water and 15% by mass of ammonia water to obtain a slurry having an alumina concentration of 12.0% by mass and a pH of 0.5. This slurry was placed in a stainless steel aging tank equipped with a refluxer and aged at 95 ° C. for 8 hours with stirring. Next, pure water was added to the aging slurry, diluted to an alumina concentration of 9.0% by mass, transferred to an autoclave equipped with a stirrer, and aged at 145 ° C. for 5 hours. Further deammoniation simultaneously heated concentrate to obtain 20 mass% in terms of Al ₂ O ₃ concentrations to obtain an alumina slurry A. The catalyst was prepared by adding 3200 g of iron-containing crystalline aluminosilicate slurry I (30.5 mass% concentration) and 2625 g of alumina slurry A (20 mass% concentration) to a kneader and extruding while heating and stirring. And then extruded into a 1 / 16-inch size trilobal pellet. Subsequently, after drying at 110 degreeC for 16 hours, it baked at 550 degreeC for 3 hours, and obtained the support | carrier A3 of 50/50 by iron containing crystalline aluminosilicate / alumina (solid content conversion mass ratio).

Next, a suspension of molybdenum trioxide and nickel carbonate in pure water was heated to 90 ° C., and then malic acid was added and dissolved. The solution is impregnated on the carrier A3 so that the total amount of the catalyst is 10.0% by mass as MoO _{3 and} 4.25% by mass as NiO, dried, calcined at 550 ° C. for 3 hours, and hydrocracked. A catalyst was obtained. This hydrocracking catalyst had a specific surface area of 455 m ² / g, a pore volume of 0.62 cc / g, and a pore volume of 0.13 cc / g with a pore diameter of 1000 mm or more. The specific surface area was measured by the BET method, the pore volume, and the pore distribution were measured by the mercury intrusion method.

[Example 5]
The HLCO fraction of Example 1 (2-ring + 3-ring / total aromatic content ratio 75%) was used.
Reaction conditions: temperature 390 ° C., hydrogen partial pressure 7 MPa, LHSV 0.6 hr ⁻¹

[Example 6]
The HLCO fraction of Example 2 (2-ring + 3-ring / total aromatic content ratio 83%) was used.
Reaction conditions: same as Example 5

[Comparative Example 4]
The LCO of Comparative Example 1 (2-ring + 3-ring / total aromatic content 65%) was used.
Reaction conditions: same as Example 5

[Comparative Example 5]
In Comparative Example 4, the reaction conditions were as follows.
Reaction conditions: temperature 390 ° C., hydrogen partial pressure 7 MPa, LHSV ¹ hr ⁻¹

[Comparative Example 6]
In Comparative Example 4, the reaction conditions were as follows.
Reaction conditions: temperature 380 ° C., hydrogen partial pressure 7 MPa, LHSV ¹ hr ⁻¹
Table 3 below shows the properties of the samples of Examples 5 and 6 and Comparative Examples 4 to 6 after hydrodesulfurization treatment and hydrocracking treatment.
The decomposition rate is a conversion rate from a boiling point of 190 ° C. to a light fraction calculated from the liquid yield in gas chromatography (ASTM D2887) and bench test. In Table 3, the aromaticity selectivity having 8 carbon atoms and the aromatic content / total aromatic content having 8 carbon atoms are values based on the weight of heavy naphtha (heavy naphtha has a boiling point of 7 or more carbon atoms). This is a fraction up to 190 ° C). In addition, the FID gas chromatography method (JIS K2536-2 “total composition analysis of gasoline”) was used for the composition analysis of aromatics.

  FIG. 3 is a graph showing the relationship between the ratio of aromatics having 8 carbon atoms / total aromatics obtained from Table 3 and the decomposition rate. As can be seen from FIG. 3, the higher the ratio of 2-ring + 3-ring / total aromatic content before hydrocracking treatment, the higher the selectivity of the aromatic component having 8 carbon atoms. Therefore, when the bicyclic or tricyclic aromatic component is used as a raw material, an aromatic component having 8 carbon atoms can be obtained in a high yield.

  INDUSTRIAL APPLICABILITY The present invention can be used as a method for producing useful ultra-low sulfur fuel oil from cracked light oil (LCO) distilled with a catalytic cracking (FCC) apparatus.

Schematic which shows the manufacturing apparatus of the ultra-low-sulfur fuel oil concerning one Embodiment of this invention. The graph which shows the relationship between the composition ratio of the aromatic part contained in a LCO fraction, and distillation temperature. The graph which shows the relationship between a C8 aromatic content and a decomposition rate from the result obtained by Test 3 of an Example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... Separation apparatus 20 ... 1st hydrodesulfurization apparatus 30 ... 2nd hydrodesulfurization apparatus 40 ... Hydrocracking apparatus

Claims (7)

An ultra-low sulfur fuel oil production method for producing ultra-low sulfur fuel oil from cracked light oil (LCO: Light Cycle Oil) distilled by fluid catalytic cracking of hydrocarbon oil,
The LCO is composed of a light cracked gas oil fraction in which the ratio of monocyclic aromatics is 0.5 to 1.0 with respect to the total aromatics, and the ratio of bicyclic and tricyclic aromatics to total aromatics. in a heavy cracked gas oil fraction is 0.5 to 1.0 relative to the minute, the separation step of separating by setting the cut temperature of the light cracked gas oil fraction in the range of 200 ° C. or higher 290 ° C. or less When,
A first desulfurization step of producing a first light oil base material by mixing a straight-run gas oil with the light cracked gas oil fraction distilled in the separation step and performing a hydrodesulfurization treatment;
A second desulfurization step for producing a desulfurized heavy cracked light oil by desulfurizing the heavy cracked light oil fraction separated in the separation step; a gasoline base material and a second light oil by cracking the desulfurized heavy cracked light oil; A method for producing an ultra-low sulfur fuel oil, comprising: a decomposition step for producing a base material. In the manufacturing method of the ultra-low sulfur fuel oil of Claim 1,
The method for producing an ultra-low sulfur fuel oil, wherein the mixing ratio of the straight-run gas oil is 40 to 80% by volume. In the manufacturing method of the ultra-low-sulfur fuel oil of Claim 1 or Claim 2,
The first desulfurization step is performed at a hydrogen partial pressure of 2 MPa or more and 10 MPa or less, and using a hydrodesulfurization catalyst containing at least one of Group 6, 8, 9, and 10 metals of the periodic table. A method for producing an ultra-low sulfur fuel oil, characterized by performing hydrodesulfurization treatment. In the manufacturing method of the ultra-low sulfur fuel oil in any one of Claims 1-3,
The second desulfurization step is performed at a hydrogen partial pressure of 5 MPa or more and 15 MPa or less, and using a hydrodesulfurization catalyst containing at least any one of Group 6, 8, 9, and 10 metals of the periodic table. A method for producing an ultra-low sulfur fuel oil, characterized by performing hydrodesulfurization treatment. In the manufacturing method of the ultra-low sulfur fuel oil in any one of Claims 1-4,
The cracking step includes performing a hydrocracking treatment using a hydrocracking catalyst containing a metal of Group 6 and Group 8 of the periodic table and further containing a crystalline aluminosilicate. Oil production method. In the manufacturing method of the ultra-low-sulfur fuel oil according to claim 5,
The method for producing an ultra-low sulfur fuel oil, wherein the crystalline aluminosilicate is a Y-type zeolite and contains iron. In the manufacturing method of the ultra-low sulfur fuel oil of Claim 5 or Claim 6,
The hydrocracking catalyst contains the crystalline aluminosilicate in an amount of 10% by mass to 80% by mass.

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