KR20060063685A - Base material for gas oil and gas oil and method of producing the same - Google Patents

Abstract

(Problem) From the petroleum-based raw material which can be supplied sufficiently, the light oil base material and light oil which reduced PAH with high unit risk by the manufacturing process with low energy consumption are provided.

(Solution) Hydrogen purification is carried out using at least one catalyst containing a porous body containing Ni and Mo as the active metal element, and the total aromatic content is 10-20 vol%, and the aromatic content of two or more rings is 0.5-1.5 vol. %, 90% by volume effluent temperature is 320-360 ° C., sulfur is 10 mass ppm or less, benzo [a] anthracene, chrysene, benzo [b] fluoranthene, benzo [k] fluoranthene, as a high unit risk compound, The total amount of benzo [a] pyrene, indeno [1,2,3-c, d] pyrene and dibenzo [a, h] anthracene is integrated in less than 0.1 massppm as 0 massppm and is 0.2 massppm or less. Get

Light oil

Description

Light oil base material and light oil, and a manufacturing method thereof BASE MATERIAL FOR GAS OIL AND GAS OIL AND METHOD OF PRODUCING THE SAME

[Patent Document 1] Japanese Unexamined Patent Publication No. 2004-067906

[Patent Document 2] Japanese Unexamined Patent Publication No. 2001-064657

[Patent Document 3] Japanese Unexamined Patent Publication No. 2000-198990

[Non-Patent Document 1] New Jersey Environmental Bureau, “UNIT RISK FACTORS FOR INHALATION” (April 2003).

TECHNICAL FIELD This invention relates to a light oil base material and a light oil, and their manufacturing method. Specifically, It is related with the light oil base material and light oil which reduced polycyclic aromatic with high unit risk, and the said light oil base material and light oil manufacturing method.

Nowadays, reduction of polycyclic aromatics (PAH) contained in diesel fuel, which is a fuel of a diesel engine, is required. On the other hand, the method (method 1) which manufactures light oil from the raw material which does not contain aromatic content like Fischer-Tropsch (FT) synthetic light oil, or nuclear hydrogenation of petroleum diesel distillate, removes aromatics How to do it (Method 2) is being reviewed.

Since the said method 1 is manufactured from the raw material which does not contain an aromatic component, it can manufacture the diesel fuel which does not contain PAH, but also has the drawback that supply of a raw material is limited and synthesis cost is high.

On the other hand, the said method 2 uses diesel fuel, such as consuming large quantities of hydrogen in order to carry out nuclear hydrogenation, treating diesel diesel distillate under high pressure hydrogen coexistence, and hydrogenating the refined diesel diesel distillate once again. There is a drawback that the investment in equipment and manufacturing costs for the production of the product increases. However, at present, since diesel is mainly produced by hydrorefining petroleum distillates, the method 2 is practical in view of the economical efficiency of using existing equipment and the balance of petroleum products, which are industrial products.

As for the method 2, various techniques have been tried to reduce the PAH contained in the diesel. For example, Patent Document 1 below discloses a gas oil composition having reduced PAH, and relates to a gas oil having reduced total PAH to 2 vol% or less, and does not mention the unit risk of PAH. As described above, the conventional PAH reduction technique is mostly focused on the method of reducing the overall PAH, and focuses on the individual unit risks of PAH, in particular, the reduction of PAH with high operational security and unit risk. The technique focusing on balance is not known.

Moreover, although the following patent document 2 is known as a manufacturing method of the light oil which reduced PAH, it is only mentioned about the effect of reducing the whole PAH here, and also economical operation is difficult in that the amount of hydrogen introduced is very large. .

Moreover, in the following patent document 3, PAH is reduced by the method of diluting a light oil distillate with the oil already hydrogenated by another apparatus and carrying out a hydrogenation process, and then hydroprocessing only the liquid distillation using a gas-liquid separator. This is also a technique for reducing the overall PAH, and new equipment investment is required, for example, a gas-liquid separation device needs to be installed downstream of the normal hydrogenation and purification apparatus.

On the other hand, with respect to the individual substances of PAH, attempts have been made to evaluate the effect on health from the viewpoint of unit risk, and the following non-patent document 1 describes the unit risk of various chemical substances. In Non-Patent Document 1, benzo [a] anthracene, chrysene, benzo [b] fluoranthene, benzo [k] fluoranthene, benzo [a] pyrene, and indeno [3] as PAH have high unit risk. 1,2,3-c, d] pyrene and dibenzo [a, h] anthracene (hereinafter referred to as high unit risk compound) are described. In contrast, acenaphthylene, acenaphthene, fluorene, anthracene, phenanthrene, fluoranthene, benzo [g, h, i] perylene and pyrene are known to have relatively low unit risk in PAH.

Under these circumstances, the problem to be solved by the present invention is to provide a gas base material and a gas oil having a low unit risk PAH from a petroleum-based raw material that can be sufficiently supplied, and a production method thereof. Is in.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, it is possible to reduce PAH with a high unit risk by performing appropriate hydrogenation and refinement | purification with respect to the diesel distillate which is not processed to reduce aromatics. To the present invention.

That is, the light oil base material and the light oil of the present invention are (1) a light oil base material and a light oil having reduced polycyclic aromatics having a high unit risk by performing hydrogenation purification of appropriate security, and the total aromatic content is 10 to 20 vol%, two or more rings. Aromatic content is 0.5-1.5 vol%, 90 volume% The outflow temperature is 320-360 degreeC, sulfur content is 10 mass ppm or less, and the total amount of a high unit risk compound is 0.2 mass ppm or less. Wherein the high unit risk compound is benzo [a] anthracene, chrysene, benzo [b] fluoranthene, benzo [k] fluoranthene, benzo [a] pyrene, indeno [1,2,3-c, d] pyrene, dibenzo [a, h] anthracene, and less than 0.1 mass ppm are integrated as 0 mass ppm.

As a reference for setting the security of the hydrorefining, the total amount of the low unit risk compound in the diesel oil distillate after hydrorefining is preferably 0.1 to 1.5 mass ppm. Here, the low unit risk compound is acenaphthylene, acenaphthene, fluorene, anthracene, phenanthrene, fluoranthene, benzo [g, h, i] perylene, and less than 0.1 mass ppm is integrated as 0 mass ppm. In particular, it is preferable that the total aromatic content calculated by the HPLC method is 13-18 vol%, and a pyrene content is 5-15 mass ppm.

In addition, the light oil base material and the light oil production method of the present invention are (2) a method for producing the light oil distillate and at least one catalyst containing a porous body (NiMo catalyst) containing nickel and molybdenum as active metal elements. Petroleum-derived distillate derived from petroleum, which has not been subjected to aromatics reduction, to be hydrolyzed and has a liquid space velocity (LHSV) of 0.1 to 2.0 h ^{- 1} , particularly 0.3 to 1.5 h- ¹ . It is preferable to carry out on condition. The distillate obtained by this method can be used as light oil as it is, and can also be mixed with another base material using this distillate as a light oil base material, and it can also be set as light oil.

To practice the invention  Best form for

EMBODIMENT OF THE INVENTION Below, this invention is demonstrated in detail. The light oil base material and the light oil of the present invention are light oil base materials and light oils which reduce PAH having high unit risk by performing hydrogenation purification of appropriate security, and the total aromatic content is 10-20 vol%, and the aromatic content of two or more rings is 0.5-1.5 vol. %, 90% by volume effluent temperature is 320 ~ 360 ℃, sulfur content is characterized in that less than 10 massppm, the total amount of the high unit risk compound is less than 0.2 massppm. Wherein the high unit risk compound is benzo [a] anthracene, chrysene, benzo [b] fluoranthene, benzo [k] fluoranthene, benzo [a] pyrene, indeno [1,2,3-c, d ] Pyrene and dibenzo [a, h] anthracene, and the total amount of the high unit risk compound is a value obtained by integrating the amount of each high unit risk compound with less than 0.1 mass ppm as 0 mass ppm. As a reference for setting the security of the hydrorefining, the total amount of the low unit risk compound in the diesel oil distillation after the hydrorefining is preferably 0.1 to 1.5 mass ppm. Wherein the low unit risk compound is acenaphthylene, acenaphthene, fluorene, anthracene, phenanthrene, fluoranthene, benzo [g, h, i] perylene, and the total amount of the low unit risk compound is less than 0.1 mass ppm. It is the value which totaled the quantity of each low unit risk compound as 0 mass ppm. Here, the measuring method of PAH is quantitatively determined by the gas chromatograph-mass spectrometer (GC-MS) about individual PAH. This method can quantify a specific component with high sensitivity by using a selective ion detection method (SIM) which detects and measures only selected ions unique to the component.

When hydrogenated and refine | purified by appropriate security, benzo [a] anthracene etc. which are high unit risk compounds can be reduced to below a measurement limit. As described in Non-Patent Document 1, benzo [a] anthracene and the like have a unit risk about 100 times higher than fluorene and phenanthrene. By substantially reducing the substance having such a high unit risk, it is possible to reduce the proportion of the high unit risk compound contained in the particulate matter (PM) generated after diesel fuel combustion, and the environmental load imparted by steam released during oil supply. In addition, when the security is increased and the low unit risk compounds such as fluorene and phenanthrene are excessively reduced, the total aromatic content is lowered, thereby reducing the rubber swelling property of the fuel tank seal, which causes a loss of fuel supply to the engine and fuel leakage. There is a case. In addition, in the case of mild hydrogenation and purification, PAH may be reduced, but in this case, since the impurity concentration such as sulfur is high, sulfur oxides contained in the combustion gas poison the catalyst used for PM reduction in the exhaust gas. V) to lower the PM removal ability of the catalyst or to shorten the catalyst life.

The total aromatic content here can be measured by type analysis of hydrocarbons (petroleum society standard JPI-5S-49-97) by HPLC method. As for the light oil base material and light oil of this invention, it is preferable that the total aromatic content measured by this method is 10-20 vol%, and is 13-18 vol%. In addition, the light oil base material and light oil of this invention are 0.5-1.5 vol% of aromatics of 2 or more rings. When leaving the aromatic content of the range shown here, the rubber swelling property of the said fuel tank seal cannot be maintained. Moreover, it is preferable that the light oil base material and the light oil of this invention are 90-300 degreeC outflow temperature, 320-360 degreeC, and 330-350 degreeC. If the 90% by volume outlet temperature is less than 320 ° C., there is no effect of adding a fluidity improver, and if it is higher than 360 ° C., the amount of PAH contained in the light oil base material and light oil increases or the amount of PM in the exhaust gas increases due to deterioration in combustibility. Adverse effects such as In addition, the light oil base material and the light oil of the present invention have a sulfur content of 10 massppm or less, preferably 5 massppm or less, and particularly preferably 3 massppm. When sulfur content is 10 mass ppm or less, the lifetime of the catalyst used for PM reduction in exhaust gas can be extended.

The above-mentioned appropriate security means that the LHSV is 0.1 to 2.0 h using at least one catalyst containing a NiMo catalyst for the hydrogenation of petroleum-derived diesel distillate which has not been specifically reduced in aromatics. ^- it indicates that performed in the ^first condition, of preferably 0.3 ~ 1.5 h ^-1 conditions.

Examples of petroleum-derived distillates derived from petroleum that have not been subjected to aromatic reduction include hydrocarbon oils having a sulfur content of at least 0.5 mass% and a 90% by volume distillation temperature of 390 ° C or less, and synthetic light oils and vegetable oil methyl esters derived by the FT method or the like. It does not contain hydrocarbon oil derived from non-petroleum. Usually, 0.5-5 mass% is preferable, and, as for the sulfur content of the petroleum-derived diesel oil distillate (henceforth raw material oil) which is not subjected to aromatic reduction treatment, 0.7-3 mass% is especially preferable. In addition, as for the nitrogen content of raw material oil, 50 mass ppm or more is preferable normally, and 80-500 mass ppm is especially preferable. The density (15 ° C) of the raw material oil is preferably 0.795 g / cm 3 or more, and more preferably 0.80 to 0.92 g / cm 3. There are no particular restrictions on the origin of hydrocarbon oil, as long as the conditions described above are satisfied, but it is preferable to use a raw material oil having a direct flow of direct-current diesel distillate alone or a crude oil having a direct-current diesel diesel distillate as a main component. Moreover, you may mix and use the process oil obtained from various petroleum refining processes with direct current diesel oil distillate. The direct current diesel oil distillate is obtained by atmospheric distillation of crude oil, and approximately 10 volume% distillation temperature is 150-280 degreeC, 50 volume% distillation temperature is 240-320 degreeC, and 90% volume distillation temperature is 300-390 degreeC. Examples of the process oil which can be mixed into the direct current diesel oil distillate to form the raw material oil include, for example, pyrolysis oil, catalytic cracking oil, direct desulfurized light oil, and indirect desulfurized light oil.

The said pyrolysis oil is a light distilled milk obtained by the reaction which mainly heats heavy oil distillate, and mainly uses a radical reaction, and means the distilled powder obtained by the delayed coking method, the bisbreaking method, the flood coking method, etc., for example. . Although these distillate may use the total distillate obtained as a pyrolysis oil, it is preferable to use the distillate in which the outflow temperature exists in the range of 150-390 degreeC.

The catalytic cracking oil is a distillate obtained when catalytically cracking an intermediate distillate, a heavy distillate, a reduced pressure diesel gas distillate, an atmospheric distillation residual oil, or the like with a zeolite catalyst, in particular, a fluid catalytic cracking apparatus for the purpose of producing high octane gasoline. It is a decomposed light oil distillate that is produced by-product. Generally, this distillate is separately collected from light catalytic cracked oil having a relatively low boiling point and heavy catalytic cracked oil having a relatively high boiling point. In the present invention, any of these distillates can be used, but it is preferable to use the former light catalytic cracking oil, so-called light cycle oil (LCO). This LCO generally has a 10 vol% outflow temperature of 210 to 250 ° C., a 50 vol% outflow temperature of 260 to 290 ° C., and a 90 vol% outflow temperature of 310 to 370 ° C. On the other hand, heavy catalytic cracking oil, so-called heavy cycle oil (HCO), usually has a 10 vol% outflow temperature of 280 to 340 ° C, a 50 vol% outflow temperature of 390 to 420 ° C, and a 90 vol% outflow temperature of 450 ° C or more, HCO is further distilled and the light distillate is mixed with the raw material oil, and the amount to be mixed with the raw material oil so that the 90 volume% effluent temperature of the diesel fuel base material of this invention and the raw material oil used for manufacture of a diesel oil becomes 390 degreeC or less. It is desirable to limit.

The direct desulfurization light oil is a diesel oil distillate produced by-product when hydrorefining the atmospheric residual oil and / or the vacuum residual oil by a direct desulfurization apparatus. In addition, the said indirect desulfurization diesel oil is a diesel gas distillate which is a by-product produced when hydrorefining the vacuum gas distillate with a indirect desulfurization apparatus. Even when these direct desulfurized and indirect desulfurized light oils are part of the raw material oil, the raw oil used in the production of the diesel oil and the diesel oil base material of the present invention is appropriately distilled and fractionated so that the 90% by volume outflow temperature is 390 ° C or lower. It is preferable to limit the amount to mix.

The hydrogenation purification carried out by the process for producing the diesel oil and gas oil base material of the present invention is not particularly limited to the reaction type such as batch type, flow type, fixed bottom type, fluidized bottom type, etc. It is preferable to supply hydrogen and raw material oil continuously in contact with each other.

Hydrogenation refining in this invention is performed on reaction conditions of reaction temperature of 280-450 degreeC, Preferably 300-420 degreeC, and hydrogen pressure of 3-10 MPa, Preferably 4-9 MPa. If the hydrogen pressure is lower than 3 MPa, it is difficult to reduce the sulfur content in the diesel fuel and the diesel fuel containing PAH having a high unit risk to 10 mass ppm or less. If the hydrogen pressure exceeds 10 MPa, the diesel fuel substrate having the high unit risk and the diesel fuel and the unit of diesel fuel are reduced. The amount of calorific value per volume is undesirable, which is undesirable. Hydrogenation refining in the present invention is preferably an LHSV 0.1 ~ 2 h ^-1, particularly preferably 0.3 ~ 1.5 h ^- is performed at the reaction conditions of the ^first. If the LHSV is less than 0.1 h ⁻¹ , the gas oil base material having a reduced amount of PAH having a high unit risk and the reaction apparatus for producing the diesel oil are too large, and if the LHSV exceeds 2 h ^{− 1} , the PAH having a high unit risk is reduced. It is not preferred that the sulfur content of one gas oil base material and light oil is less than 10 mass ppm.

In addition, the hydrogenation purification in this invention is performed on reaction conditions of 100-1000 NL / L of hydrogen / oil ratio, Preferably it is 150-500 NL / L. When the hydrogen / oil ratio is less than 100 NL / L, it is difficult to reduce the sulfur content of the gas oil base material and diesel oil having a low unit risk PAH to 10 mass ppm or less, and when the hydrogen / oil ratio exceeds 1000 NL / L, the cost of hydrogen supply becomes high. In addition, it is not preferable to manufacture a diesel fuel base material and a diesel fuel oil having a low unit risk, which has a high economic risk. When hydrorefining is carried out in a fixed-bottom flow reactor, the hydrorefining catalyst may be charged in a single catalyst bottom or may be divided and filled in two or more catalyst bottoms. In the case of dividing into two or more catalyst bottoms to charge a hydrogenation catalyst, it is preferable to supply quench hydrogen between the catalyst bottoms. When quench hydrogen is supplied between the catalyst bottoms, it is preferable to set the ratio of the total amount of hydrogen and quench hydrogen supplied with the raw material oil to the reactor inlet and the supply amount of the raw material oil to 100 to 1000 NL / L, and 150 to 500 NL It is especially preferable to set it as / L.

The hydrorefining catalyst used for the diesel fuel base material and the diesel fuel manufacturing method which reduced PAH with high unit risk of this invention consists of at least 1 type of catalyst containing a NiMo catalyst. The NiMo catalyst referred to herein is a porous body containing nickel and molybdenum as an active metal element, preferably 1 to 10 mass% of nickel and 2 to 30 mass% of molybdenum. Moreover, the hydrogenation purification catalyst may contain elements, such as phosphorus, boron, and fluorine. Further, hydrogenated tablets containing chelating organic compounds such as ethylenediaminetetraacetic acid (EDTA), trans-1,2-cyclohexanediamine-N, N, N ', N'-4acetic acid, nitrilotriacetic acid and citric acid Catalysts are also preferably used. The hydrogenation refining catalyst used for the gas oil base material which reduced PAH of high unit risk of this invention, and the method of manufacturing a gas oil has the median pore diameter of mesopoa, Preferably it is 4-20 nm, More preferably, it is 4-15 nm. Moreover, specific surface area becomes like this. Preferably it is 30-800 m <2> / g, More preferably, it is 50-600 m <2> / g. It is preferable that the hydrorefining catalyst used for the light oil base material and the manufacturing method of light oil which reduced PAH with high unit risk of this invention is not a powder but a molded object. Although there is no restriction | limiting in particular in the shape of a molded object and the shaping | molding method, A spherical shape or a columnar shape is preferable. In the case of a spherical shape, the diameter is preferably 0.5 to 20 mm. In addition, the cross-sectional shape in the case of columnar shape is not particularly limited, but a circular shape, a three leaf shape, and a four leaf shape are preferable. It is preferable that the dimension of the molded object in the case of columnar shape is about 0.25-400 mm <2> and about 0.5-20 mm in length in cross section. Although there is no restriction | limiting in particular in the manufacturing method of the said hydrogenation refining catalyst, It is preferable to make it contain the addition inorganic elements, such as the above-mentioned active metal element, phosphorus, etc. in a porous inorganic oxide support. Examples of the porous inorganic oxide include oxides such as alumina, silica, titania, magnesia and zirconia, silica-alumina, silica-titania, silica-zirconia, silica-magnesia, silica-alumina-titania, silica-alumina-zirconia, and the like. It is preferable that it consists of 1 type (s) or 2 or more types chosen from zeolites, such as a zeolite, stabilized Y zeolite, (beta) zeolite, a mordenite zeolite, and MCM-22.

In addition, in the light oil base material and the light oil manufacturing method which reduced PAH with high unit risk of this invention, you may laminate | stack and use in combination with 1 or more types of hydrogenation purification catalysts other than a NiMo catalyst. Hydrogen purifying catalysts in combination with NiMo catalysts are porous metals containing molybdenum and / or tungsten and cobalt and / or nickel as active metal elements, such as CoMo catalysts, NiCoMo catalysts, NiW catalysts, and the like. The content is 1 to 10 mass%, and the content of molybdenum and tungsten is 2 to 30 mass%. In addition, the hydrorefining catalyst combined with a NiMo catalyst may contain elements, such as phosphorus, boron, and fluorine. Further, hydrogenated tablets containing chelating organic compounds such as ethylenediaminetetraacetic acid (EDTA), trans-1,2-cyclohexanediamine-N, N, N ', N'-4acetic acid, nitrilotriacetic acid and citric acid Catalysts are also preferably used. The hydrogenation refining catalyst used for the gas oil base material which reduced PAH with high unit risk of this invention, and the method of manufacturing light oil has the median pore diameter of mesopoa, Preferably it is 4-20 nm, More preferably, it is 4-15 nm. Moreover, specific surface area becomes like this. Preferably it is 30-800 m <2> / g, More preferably, it is 50-600 m <2> / g. It is preferable that the hydrorefining catalyst used for the light oil base material and the manufacturing method of light oil which reduced PAH with high unit risk of this invention is not a powder but a molded object. Although there is no restriction | limiting in particular in the shape of a molded object and the shaping | molding method, spherical shape or columnar shape is preferable. In the case of a spherical shape, the diameter is preferably 0.5 to 20 mm. In addition, the cross-sectional shape in the case of columnar shape is not particularly limited, but a circular shape, a three leaf shape, and a four leaf shape are preferable. It is preferable that the dimension of the molded object in the case of columnar shape is about 0.25-400 mm <2> and about 0.5-20 mm in length in cross section. Although there is no restriction | limiting in particular in the manufacturing method of the hydrorefining catalyst combined with the said NiMo catalyst, It is preferable to make it, the porous inorganic oxide support | carrier containing the above-mentioned addition element, such as an active metal element or phosphorus, and manufacturing. Examples of the porous inorganic oxide include oxides such as alumina, silica, titania, magnesia and zirconia, silica-alumina, silica-titania, silica-zirconia, silica-magnesia, silica-alumina-titania, silica-alumina-zirconia, and the like. It is preferable that it consists of 1 type (s) or 2 or more types chosen from zeolites, such as a zeolite, stabilized Y zeolite, (beta) zeolite, a mordenite zeolite, and MCM-22.

4-position of dibenzothiophene (DBT), such as 4-methyldibenzothiophene (4-MDBT), 4,6-dimethyldibenzothiophene (4,6-DMDBT) contained in the diesel distillate; It is known that a sulfur compound having an alkyl substituent which is a steric hindrance to a sulfur atom at the 6-position is known and is called a desulfurization sulfur compound [T.Kabe, A.Ishihara, W.Quin, “Hydrodesulfurization and Hydrodenitrogenation” , Kodansha (1999)]. Therefore, the hydrorefining of the diesel diesel distillate causes selective desulfurization sulfur compounds to remain selectively. On the other hand, desulfurization of such desulfurized sulfur compounds includes desulfurization reaction routes after hydrogenation of benzene rings in the DBT skeleton to alleviate steric hindrance by substituents, rather than directly desulfurization of sulfur atoms in the DBT skeleton (direct desulfurization route). It is known to use a hydrogenation purification catalyst which is easy to take the desulfurization route). In addition, when the cobalt-molybdenum-based hydrorefining catalyst and the nickel-molybdenum-based hydrorefining catalyst are compared, the latter is known to easily take the hydrodesulfurization route. Therefore, when two or more types of hydrorefining catalysts are combined and laminated in a reaction apparatus, a smaller proportion of nickel in the total content of cobalt and nickel contained in the hydrorefining catalysts is smaller at the inlet of the reactor where the raw material oil is supplied. On the closer side, it is preferable to arrange | position the one with a larger ratio of nickel to the total content of cobalt and nickel on the side closer to a reactor outlet.

According to the light oil base material and the light oil manufacturing method which reduced PAH with high unit risk of this invention, the obtained light oil distillate can be used as it is as light oil which reduced PAH with high unit risk, or mixed with another base material, It can also be used as a gas oil base material for preparing the gas oil product which reduced high PAH. As another gas oil base material to be mixed with the gas oil base material of the present invention, for example, kerosene produced by refining crude oil, synthetic light oil derived by Fischer-Tropsch method, etc., a base for compounding such as semi-finished products, intermediate products, etc. Can be mentioned. Still, vegetable oil methyl ester, ethers and the like can also be blended as other light oil base materials. In the case where the light oil base material of the present invention is mixed with another light oil base material to prepare a light oil having a low unit risk of the present invention, PAH can be appropriately blended so as to have light oil of desired quality, but the mixing ratio of the other light oil base material is 20 mass. It is preferable to set it as% or less, and it is especially preferable to set it as 15 mass%.

Moreover, in the manufacturing method of the diesel fuel which reduced PAH with high unit risk of this invention, even if it adds well-known fuel additives, such as a low-temperature fluidity improver, an abrasion resistance improver, a cetane number improver, antioxidant, a metal deactivator, and a corrosion inhibitor, do. An ethylene copolymer or the like can be used as the low temperature fluidity improver, and vinyl esters of saturated fatty acids such as vinyl acetate, vinyl propionate and vinyl butyrate are particularly preferably used. In addition, as the wear resistance improving agent, a long chain fatty acid or a fatty acid ester thereof (for example, 12 to 24 carbon atoms) is preferably used, and the wear resistance can be sufficiently improved by an addition amount of 10 to 500 massppm, preferably 50 to 100 massppm.

EMBODIMENT OF THE INVENTION Although this invention is demonstrated concretely based on an Example below, this invention is not limited at all by this.

Example

PAH of the hydrorefining process product oil mentioned later was measured by the method of describing below.

(PAH measurement pretreatment)

After weighing a certain amount of the sample, a solution dissolved with n-heptane was injected into an alumina cartridge column. Next, the PAH component hold | maintained in the alumina column was eluted with toluene, the eluted toluene solution was eluted at 1 mL with toluene, and it was set as the measurement solution.

(GC-MS (SIM) measurement)

PAH was quantified with the following apparatus and conditions.

GC unit: 6890N type GC manufactured by Agilent

Detector: 5973N type quadrupole mass spectrometer manufactured by Agilent

Column: HP-5MS from Agilent

Liquid: 95% Dimethylpolysiloxane-5% Diphenylpolysiloxane

Column size: inner diameter 0.25mm x 30m, film thickness = 0.25 micron

Column oven temperature: 70 ° C. (10 min hold) → 10 ° C./min, elevated temperature 300 ° C. (17 min hold)

Inlet temperature: 290 ℃

Transfer Line Temperature: 290 ℃

Detector temperature: Ion source temperature = 230 ° C, quadrupole temperature = 150 ° C

Column flow rate: 0.7 mL

Carrier Gas: Helium

Injection method: pulse splitless, pulse pressure at injection = 25psi (1.5min)

Split vent line: 50 mL (1.5 min)

SIM condition (quantitative ion)

Acenaphthylene = 152, acenaphthene = 154, fluorene = 166, phenanthrene and anthracene = 178, fluoranthene and pyrene = 202, benzo [a] anthracene and chrysene = 228, benzo [b] fluoranthene, benzo [k] fluoranthene, benzo [a] pyrene = 252, benzo [g, h, i] perylene, indeno [1,2,3-c, d] pyrene = 276, dibenzo [a, h] Anthracene = 278.

(Example 1)

100 mL of hydrogenation purification catalyst HOP-414 (NiMo catalyst, ART KK) was charged to a fixed-bottom flow reactor, and the temperature was raised from room temperature to 150 ° C. while flowing hydrogen at a hydrogen pressure of 5.0 MPa and 10 L / h. The catalyst was presulfurized in the following procedure. Sulfurizing agent (combined with 1 mass% carbon bisulfide in commercially available diesel oil) was passed through a hydrogen pressure of 5.0 MPa, hydrogen / oil ratio 500NL / L, LHSV = 2.0 h ^-1 and 150 ° C for 2 hours. ) Then, conditions other than temperature were made constant, supply of sulfiding agent and hydrogen was continued, it heated up from 20 degreeC / h to 230 degreeC, and made it constant at 230 degreeC for 4 hours. Thereafter, the temperature was further raised from 17.5 ° C / h to 300 ° C, and the temperature was constant at 300 ° C for 4 hours. Thereafter, hydrogenation purification reaction of the following diesel oil distillate A (Table 1) was performed using this sulfided hydroprocessing catalyst. The hydrogenation purification reaction was performed at a hydrogen pressure of 8.0 MPa, a hydrogen / raw oil feed ratio of 300 NL / L, LHSV = 1.2 h ⁻¹ and a reaction temperature of 352 ° C. The total amount of the high unit risk compound contained in the obtained product oil was 0 mass ppm, and the sulfur content in the product oil was 1.3 mass ppm. In addition, the total amount of the low unit risk compound contained in the product oil was 1.1 mass ppm, and the pyrene content was 8.7 mass ppm (Table 2).

(Example 2)

The hydrogenation and purification reaction was carried out by the same apparatus, operation procedure, raw material oil and catalyst as in Example 1, except that the hydrogen pressure was 6.5 MPa, the hydrogen / raw oil feed ratio 350NL / L, LHSV = 1.0 h ⁻¹ and the reaction temperature was 350 ° C. It was done. The total amount of the high unit risk compound contained in the obtained product oil was 0 mass ppm, and the sulfur content in the produced oil was 3.7 mass ppm. In addition, the total amount of the low unit risk compound contained in the product oil was 0.4 mass ppm and the pyrene content was 7.0 mass ppm (Table 2).

(Example 3)

15 m 3 of hydrogenation purification catalyst HOP-467 (CoMo catalyst, ART KK) and 45 m 3 of HOP-414 (NiMo catalyst, ART KK) were charged to a fixed-bottom flow reactor. The hydrogenation purification reaction of the following diesel oil distillate B (Table 1) was performed using the hydroprocessing catalyst presulfurized using DMDS. The hydrogenation purification reaction was performed at a reactor inlet hydrogen pressure of 6.8 MPa, hydrogen / raw oil feed ratio 300Nm 3 / KL, LHSV = 1.0 h ⁻¹ , and a catalyst weight average temperature of 350 ° C. The total amount of the high unit risk compound contained in the obtained product oil was 0 mass ppm, and the sulfur content in the product oil was 7.4 mass ppm. In addition, the total amount of the low unit risk compound contained in the product oil was 0.1 mass ppm and the pyrene content was 10 mass ppm (Table 2).

(Comparative Example 1)

40 m 3 of hydrogenation purification catalyst HOP-467 (CoMo catalyst, ART KK) and 20 m 3 of HOP-414 (NiMo catalyst, ART KK) were charged to the fixed-bottom flow reactor. The hydrogenation purification reaction of the following diesel oil distillate C (Table 1) was performed using the hydroprocessing catalyst presulfurized using DMDS. The hydrogenation purification reaction was performed at a reactor inlet hydrogen pressure of 5.2 MPa, a hydrogen / raw oil feed ratio of 250 Nm 3 / KL, LHSV = 2.8 h ⁻¹ and a catalyst weight average temperature of 370 ° C. The total amount of the high unit risk compound contained in the obtained product oil was 0.5 mass ppm and the sulfur content in the product oil was 38 mass ppm. In addition, the total amount of the low unit risk compound contained in the product oil was 0.7 mass ppm and the pyrene content was 9.8 mass ppm (Table 2).

(Comparative Example 2)

Hydrogen pressure 5.0 MPa, hydrogen / raw oil feed ratio 200NL / L, LHSV = 4.5 h ⁻¹ , reactor temperature 345 ° C., crude oil distillate D (Table 1), the catalyst hydrogenated refining catalyst HOP-467 (CoMo catalyst, ART KK) The hydrogenation purification reaction was performed by the apparatus and operation procedure similar to Example 1 except having made into 100 mL. Although the total amount of the high unit risk compound contained in the obtained product oil was 0 mass ppm, the sulfur content in the produced oil was 511 mass ppm. In addition, the total amount of the low unit risk compound contained in the product oil was 0 mass ppm and the pyrene content was 2.6 mass ppm (Table 2).

(Comparative Example 3)

Hydrogen pressure 5.9 MPa, hydrogen / raw oil feed ratio 170NL / L, LHSV = 0.9 h ⁻¹ , reactor temperature 345 ° C., crude oil distilled fraction E (Table 1), the catalyst was hydrogenated refining catalyst Z (CoMo A hydrogenation purification reaction was conducted in the same apparatus and operation procedure as in Example 1, except that 100 mL of the catalyst, Co: 3.5 mass%, and Mo: 15 mass%) were used. The total amount of the high unit risk compound contained in the obtained product oil was 0.3 mass ppm, and the sulfur content in the produced oil was 7.3 mass ppm. In addition, the total amount of the low unit risk compound contained in the product oil was 3.0 mass ppm and the pyrene content was 56 mass ppm (Table 2).

(Comparative Example 4)

Hydrogenation and purification were carried out in the same apparatus and operation procedure as in Comparative Example 3 except that the hydrogen / raw oil feed ratio was 200 NL / L and the reactor temperature was 355 ° C. The total amount of the high unit risk compound contained in the obtained product oil was 0.9 mass ppm, and the sulfur content in the produced oil was 5.8 mass ppm. In addition, the total amount of the low unit risk compound contained in the product oil was 1.1 mass ppm, and the pyrene content was 66 mass ppm (Table 2).

From Table 2, it can be seen that, by performing hydrogenation and purification of appropriate gas oil in Examples, PAH having a high unit risk such as benzo [a] anthracene is sufficiently reduced, and sulfur content is sufficiently low.

According to the present invention, even if the aromatics in the petroleum-based raw material are not completely removed by the above-described substrate, a diesel fuel substrate having sufficiently reduced PAH having a high unit risk such as benzo [a] anthracene by performing hydrogenation purification of appropriate security. And diesel.

Claims (10)

10-20 vol% of total aromatics, 0.5-1.5 vol% of aromatics of two or more rings, 90 vol% of extraction temperature is 320-360 ° C, sulfur is 10 massppm or less, Benzo [a] anthracene, chrysene, benzo [b] fluoranthene, benzo [k] fluoranthene, benzo [a] pyrene, indeno [1,2,3-c, as a high unit risk compound, d] The gas oil base material characterized in that the total amount of pyrene and dibenzo [a, h] anthracene is 0.2 mass ppm or less, integrating less than 0.1 mass ppm as 0 mass ppm. The total amount of acenaphthylene, acenaphthene, fluorene, anthracene, phenanthrene, fluoranthene and benzo [g, h, i] perylene as the low unit risk compound is less than 0.1 mass ppm as 0 mass ppm. Gas oil base material that is 0.1 to 1.5 massppm in total. 3. The diesel fuel substrate according to claim 2, wherein the pyrene content is 5 to 15 mass ppm. Claim 1, characterized in that hydrogenation of petroleum-derived distillate derived from petroleum not subjected to aromatic reduction treatment using at least one catalyst containing a porous body containing nickel and molybdenum as an active metal element. The manufacturing method of the light oil base material in any one of Claims 1-3. The method for producing a gas oil base material according to claim 4, wherein the hydrogenation purification is performed under the condition that the LHSV is 0.1 to 2.0 h ^{- 1} . 10 to 20 vol% of total aromatics, 0.5 to 1.5 vol% of aromatics of two or more rings, 90 vol% of outlet temperature is 320 to 360 ° C, sulfur is 10 massppm or less, Benzo [a] anthracene, chrysene, benzo [b] fluoranthene, benzo [k] fluoranthene, benzo [a] pyrene, indeno [1,2,3-c, d] pyrene as a high unit risk compound And a total amount of dibenzo [a, h] anthracene is 0.2 mass ppm or less, in which less than 0.1 mass ppm is integrated as 0 mass ppm. The total amount of acenaphthylene, acenaphthene, fluorene, anthracene, phenanthrene, fluoranthene and benzo [g, h, i] perylene as the low unit risk compound is less than 0.1 mass ppm as 0 mass ppm. Diesel oil, cumulative, from 0.1 to 1.5 massppm. 8. The diesel fuel of claim 7, wherein the pyrene content is between 5 and 15 mass ppm. Claim 6, characterized in that hydrogenation of petroleum-derived distillate derived from petroleum not subjected to aromatic reduction treatment is carried out using at least one catalyst containing a porous body containing nickel and molybdenum as an active metal element. The manufacturing method of the diesel fuel in any one of Claims 8-8. The method for producing light oil according to claim 9, wherein the hydrogenation purification is performed under the condition that LHSV is 0.1 to 2.0 h ^{- 1} .