JP2019089935A - Diesel fuel composition - Google Patents

Abstract

To provide the diesel fuel composition having a high cetane index and excellent low temperature fluidity.SOLUTION: The diesel fuel composition comprises a fuel base material A and a fuel base material B, wherein the fuel base material A is obtained by subjecting a raw material containing an animal and vegetable fat and oil and/or a component derived from the animal and vegetable fat and oil to a hydrodeoxygenation treatment and an isomerization treatment, and the fuel base material B is obtained by subjecting a mixed gas oil of a straight run gas oil (base material X) and a cracked gas oil (base material Y) to hydrotreatment.SELECTED DRAWING: None

Description

  The present invention relates to diesel fuel compositions.

The world economy relies on fossil resources such as oil for most of its energy supply. However, the continuous use of fossil resources is a factor of serious social problems symbolized by global warming and environmental pollution, and the rapid and global expansion of the industry threatens the foundation of human society development by exhaustion of fossil resources. Is bringing.
Under such circumstances, promotion of use of renewable energy instead of fossil fuel has been proposed. As renewable energy, in addition to the use of natural energy (sunlight, wind power, geothermal, etc.), the use of biomass that utilizes the capacity possessed by living beings is being considered, and technological development for practical use of these has flourished in recent years It has been done.

As a fuel using biomass, biomass fuel derived from animal and vegetable fats and oils has attracted attention. Currently, FAME (Fatty Acid Methyl Ester), which is the mainstream of biomass fuel for diesel vehicles, is a biomass fuel in which animal and vegetable fats and oils are brought close to the physical properties of light oil by transesterification. However, since FAME is a fuel having properties different from those of existing petroleum fuels, it causes various problems in the engine. For this reason, biomass fuel with better performance than FAME is desired.
As a biomass fueling technology to replace FAME, a technology for hydrorefining animal and vegetable fats and oils to obtain a light oil composition has attracted attention. As such a technique, what is described in patent documents 1-3 is known, for example.

  In Patent Documents 1 to 3, a fraction obtained by contacting a raw material containing an animal and vegetable fat and / or a component derived from an animal and vegetable fat and oil and a sulfur-containing hydrocarbon compound with a sulfide catalyst is further supported on a carrier containing crystalline molecular sieves. A gas oil composition is described which comprises a distillate which has been hydrogenated using a metal catalyst.

JP 2007-332359 A JP, 2009-161669, A Unexamined-Japanese-Patent No. 2007-308576

However, the light oil compositions described in these Patent Documents 1 have higher clogging points of -8 ° C and -12 ° C and pour points of -10.0 ° C and -12.5 ° C, respectively. It can not be said that the low temperature fluidity is excellent. The light oil composition described in Patent Document 2 has a clogging point of −15 ° C., but has a low cetane index. Moreover, the light oil composition described in Patent Document 3 has a high pour point of −12.5 to −15.0 ° C., and can not be said to be excellent in low temperature fluidity.
Then, an object of the present invention is to provide a diesel fuel composition having a high cetane index and excellent low temperature fluidity.

  MEANS TO SOLVE THE PROBLEM The present inventors discovered that it could be solved by the following invention, as a result of repeating earnest research in order to solve the said subject. That is, the present invention provides a diesel fuel composition having the following constitution.

1. Fuel base A obtained by hydrodeoxygenation of raw materials containing animal and vegetable fats and / or components derived from animal and vegetable fats and oils, and fuel base B obtained by hydrotreating a mixed gas oil of straight run gas oil and cracked gas oil A diesel fuel composition containing:
2. Furthermore, the diesel fuel composition as described in 1 above, further comprising desulfurized straight-run gas oil.
3. The diesel fuel composition according to the above 1 or 2, further comprising a low temperature fluidity improver.
4. The diesel fuel composition according to any one of the above 1 to 3, wherein the content based on the total amount of the composition of the fuel base A is 5% by volume or more and 60% by volume or less.
5. The diesel fuel composition according to any one of the above 1 to 4, wherein the content based on the total amount of the composition of the fuel base B is 10% by volume or more and 95% by volume or less.
6. The diesel fuel composition according to any one of the above 2 to 5, wherein the content based on the total amount of the composition of the desulfurized directly distilled light oil is 1% by volume or more and 65% by volume or less.
7. The diesel fuel composition according to any one of the above 1 to 6, wherein the cetane index is 55 or more, the pour point is -15 ° C or less, and the clogging point is -12 ° C or less.

  According to the present invention, it is possible to provide a diesel fuel composition having a high cetane index and excellent in low temperature fluidity.

[Diesel fuel composition]
The diesel fuel composition according to an embodiment of the present invention (hereinafter sometimes referred to simply as the present embodiment) is obtained by hydrodeoxygenating a raw material containing an animal and vegetable oil and / or a component derived from an animal and vegetable oil and isomerizing it. The fuel base A includes the treated fuel base A, and the fuel base B obtained by hydrotreating a mixed light oil of a straight run light oil (base X) and a cracked light oil (base Y).

(Fuel base A)
The fuel base material A is obtained by hydrodeoxygenating and isomerizing a raw material containing an animal and vegetable fat and / or a component derived from an animal and vegetable fat and oil.

<A raw material containing animal and vegetable fats and/or ingredients derived from animal and vegetable fats and oils>
In the present specification, animal and animal fats and oils are oils and fats obtained by squeezing animal or plant raw materials or extraction with an organic solvent, and those obtained from plants are called vegetable oils and fats, and those obtained from animals are animal fats and oils It is said that these are combined animal and vegetable fats and oils.
Examples of animal and vegetable fats and oils and / or components derived from animal and vegetable fats and oils include, for example, coconut oil, palm kernel oil, palm oil, cocoa butter, linseed oil, safflower oil, sesame seed oil, tung oil, cottonseed oil, rapeseed oil, sesame oil, corn Vegetable oil such as oil, soybean oil, sunflower oil, kapok oil, olive oil, mustard oil, peanut oil, castor oil, castor oil, camellia oil, jatropha oil, camelina oil, carinata oil, mandari oil, oil derived from microalgae, milk fat, goat Animal fats and oils such as milk fat, buffalo milk, beef tallow, pork fat, sheep fat, fish oil, liver oil, beef leg oil and the like, and animal oil and the like can be mentioned. These can be used alone or in combination of two or more.
In addition, animal and vegetable fats and / or components derived from animal and vegetable fats and oils include waste oils and fats derived from these animal and vegetable fats and oils, and waste oils obtained after using components derived from animal and vegetable fats and oils for consumer, industrial, and food applications. In this case, as the waste oil, it is preferable to use one from which foreign matters and the like have been removed.

  As the animal and vegetable fats and / or ingredients derived from animal and vegetable fats and oils, it is preferable to use vegetable fats and oils and components derived from vegetable fats and oils, in consideration of ease of handling, high productivity, etc. From the viewpoint, particularly, Jatropha oil, palm oil composition and soybean oil are preferable.

Moreover, as an animal and vegetable oil and fat and / or a component derived from an animal and vegetable oil and fat, oil derived from microalgae can also be preferably used.
The term "microalgae" in oil derived from microalgae means algae having the property of converting a part of nutrients in the body into a form of hydrocarbon or oil. Such microalgae include, for example, aulanthiochytrium, botryococcus braunii, pseudocoliosissis ellipsoida, pseudococcus victoria, chlorella, icadamo, spirulina, euglena, solaris, and nannochloropsis.

  The animal and vegetable fats and oils and / or the component derived from animal and vegetable fats and oils are mainly composed of at least one fatty acid selected from fatty acid triglyceride, fatty acid diglyceride, fatty acid monoglyceride, (free) fatty acid, and fatty acid ester and derivatives thereof. The number of carbons in the fatty acid portion of these fatty acids and their derivatives is preferably 12 or more, more preferably 16 or more, and preferably 24 or less, more preferably 18 or less as the upper limit. When the carbon number is in the above range, a high cetane index and excellent low temperature fluidity can be obtained, and the specification of light oil can be easily satisfied. Moreover, the yield of the fuel base material by hydrodeoxygenation processing can also be raised. In the present specification, numerical values relating to “or more” and “below” relating to the description of numerical ranges are numerical values that can be arbitrarily combined.

The raw material used for the fuel base material A is not particularly limited as long as it contains the above-mentioned animal and vegetable fats and / or components derived from the animal and vegetable fats and oils. As raw materials used for the fuel base material A, in addition to the above-mentioned animal and vegetable fats and / or components derived from animal and vegetable fats and oils, for example, botryocossen, squalene, carbon-carbon double thereof in which fine algae co-produces with animal and fats and oils etc. The bond may be hydrogenated or partially hydrogenated (eg, squalane etc.).
The proportion of the animal and vegetable fats and / or components derived from animal and vegetable fats and oils contained in the raw material is preferably 20% by volume or more, more preferably 30% by volume or more, still more preferably 40% by volume or more from the viewpoint of improvement in cetane index. is there. Further, the upper limit value of the above ratio is 100% by volume.

Hydrodeoxygenation treatment
The hydrodeoxygenation catalyst used for the hydrodeoxygenation treatment of the raw material is preferably one in which at least one metal selected from the elements of Groups 6A and 8 is supported on a catalyst support. Further, phosphorus may be further supported on the catalyst carrier, and phosphorus may be contained in the active metal impregnation solution.
Preferred examples of at least one metal selected from Group 6A and Group 8 elements include nickel, cobalt, molybdenum and tungsten, and combinations thereof, for example, Ni-Mo, Ni-W, Co-Mo And Ni-Co-Mo are preferably mentioned.
The supported amount of nickel or cobalt in the hydrodeoxygenation catalyst is preferably 1% by mass or more and 10% by mass or less based on the oxide, and the supported amount of molybdenum or tungsten in the hydrodeoxygenation catalyst is preferably 10% by mass. % Or more and 40% by mass or less, and the supported amount of phosphorus in the hydrodeoxygenation catalyst is preferably 1% by mass or more and 10% by mass or less.

The catalyst support preferably contains 50% by mass or more of alumina, and the alumina is preferably γ-alumina. The catalyst support may further contain titania.
The average pore size of the catalyst carrier is preferably 5 nm or more, more preferably 6 nm, and the upper limit is preferably 15 nm or less, more preferably 14 nm or less. The form of the catalyst support may be powder, or may be a compact such as a cylinder, three-leaf, four-leaf or the like.

As a method of supporting at least one metal selected from the elements of Group 6A and Group 8 on the catalyst support, an impregnation method is preferably mentioned.
The nickel compound for supporting nickel on the catalyst support by the impregnation method preferably includes at least one compound selected from nickel carbonate, basic nickel carbonate, and nickel nitrate. As the cobalt compound for supporting cobalt on the catalyst carrier by the impregnation method, preferably, one compound selected from cobalt carbonate, basic cobalt carbonate and cobalt nitrate is mentioned. As a molybdenum compound for supporting molybdenum on a catalyst carrier by an impregnation method, preferably, at least one compound selected from molybdenum trioxide and ammonium molybdate is mentioned. As a tungsten compound for supporting tungsten on a catalyst carrier by an impregnation method, preferably, at least one compound selected from tungsten trioxide and ammonium tungstate is mentioned. Moreover, as a phosphorus compound for making a catalyst support | carrier carry | support phosphorus by an impregnation method, Preferably, at least 1 type of compound chosen from phosphorus pentoxide and orthophosphoric acid is mentioned.

  The hydrodeoxygenation catalyst may be reduced under hydrogen prior to using the hydrodeoxygenation catalyst. The conditions for reduction under hydrogen are preferably a reduction temperature of 300 ° C. to 400 ° C., and a reduction time of preferably 1 hour to 36 hours.

The hydrodeoxygenation catalyst may be used after being sulfurized in the reaction system. As a method of sulfurizing a hydrodeoxygenation catalyst, for example, liquid phase sulfidation performed by mixing a sulfurizing agent such as dimethyl disulfide into the raw material and supplying the mixture into the catalyst, and an air mixture performed by supplying an H ₂ S mixed gas Phase sulfurization etc. are mentioned.

  The pressure in the hydrodeoxygenation treatment is preferably 2 MPa or more, more preferably 3 MPa or more, and the upper limit is preferably 8 MPa or less, more preferably 7 MPa or less, from the viewpoint of energy efficiency of the hydrodeoxygenation treatment and the like. The reaction temperature is preferably 250 ° C. or more, more preferably 330 ° C. or more, and the upper limit is preferably 450 ° C. or less, more preferably 400 ° C. or less.

From the same viewpoint as this, the liquid hourly space velocity (LHSV) is preferably 0.2 hr- ¹ or more, more preferably 0.3 hr- ¹ or more, and preferably 3.0 hr- ¹ or less as the upper limit. Preferably it is 2.0 hr < ^-1 > or less. The hydrogen / The oil ratio, preferably 1000 Nm ³ / kL or more, more preferably 1500 Nm ³ / kL or more, more preferably 1800 Nm ³ / kL or more, preferably not more than 3000 Nm ³ / kL upper limit, more preferably It is 2500 Nm ³ / kL or less, more preferably 2200 Nm ³ / kL or less.

<Isomerization treatment>
The step of subjecting the hydrodeoxygenated raw material to an isomerization treatment refers to a step of performing an isomerization reaction that causes a long chain hydrocarbon portion derived from the fatty acid portion of the fatty acid derivative contained in the raw material to branch. This process can improve the low temperature performance of the hydrodeoxygenated raw material.
The isomerization catalyst used for the isomerization treatment is preferably one having at least one metal selected from the elements of Groups 8 to 10 supported on a catalyst support. As an element of Groups 8 to 10 used for the isomerization catalyst, ruthenium, rhodium, palladium, osmium, iridium, a platinum group element of platinum are preferable, and in particular, palladium of Group 10 and platinum are more preferable.

  The supported amount of the metal element in the isomerization catalyst is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and the upper limit is preferably 5% by mass or less, more preferably 1.5% by mass It is.

The catalyst support is preferably a support having an acid property, and examples thereof include alumina, zeolite, silica alumina, alumina boria, alumina titania, silica zirconia, silicoaluminophosphate and the like. These carriers may be used alone or in combination of two or more.
The form of the catalyst support may be powder, or may be a compact such as a cylinder, three-leaf, four-leaf or the like.

As a method of supporting at least one metal selected from the elements of Groups 8 to 10 on the catalyst support, preferably, an impregnation method is mentioned.
As a compound containing the said metal element component used by the impregnation method, various metal salts, such as hydrochloride, a sulfate, nitrate, a complex compound, and a chloride, are mentioned. For example, when ruthenium is supported on the catalyst carrier, ruthenium chloride, ruthenium nitrate, ruthenium nitrosyl nitrate, tris (acetylacetonato) ruthenium or the like may be used as the compound containing ruthenium. When rhodium is supported on the catalyst carrier, rhodium chloride, rhodium nitrate, rhodium acetate, rhodium sulfate or the like may be used as the compound containing rhodium. When palladium is supported on the catalyst carrier, palladium chloride, sodium chloropalladate, palladium nitrate, palladium sulfate, palladium acetate, palladium propionate and the like may be used as a compound containing palladium. When osmium is supported on the catalyst carrier, osmium chloride, hexachloroosmium acid salt or the like may be used as the compound containing osmium. In the case where iridium is supported on the catalyst carrier, iridium chloride, hexachloroiridate, etc. may be used as the compound containing iridium. When platinum is supported on the catalyst support, examples of platinum-containing compounds include platinum nitrate, platinum sulfate, chloroplatinic acid, tetrachloroplatinic acid, tetraammineplatinum chloride, tetraammineplatinum nitrate, tetraammineplatinum acetate, and tetraammineplatinum carbonate. Dichlorotetraammine platinum, dinitrodiammine platinum, dinitrodiammine platinum nitrate, potassium hexachloroplatinate, etc. may be used. These compounds may be used alone or in combination of two or more.

  The isomerization catalyst may be reduced under hydrogen prior to using the isomerization catalyst. The conditions for reduction under hydrogen are preferably a reduction temperature of 200 ° C. or more, more preferably 250 ° C. or more, and an upper limit of preferably 500 ° C. or less, more preferably 400 ° C. or less. The reduction time is preferably 1 hour or more and 36 hours or less.

  In the isomerization reaction, the reaction proceeds even in the substantial absence of hydrogen, but from the viewpoint of suppressing coke deterioration of the isomerization catalyst, it is preferable to perform the isomerization reaction in the presence of hydrogen. The pressure in the isomerization treatment is preferably 1.5 MPa or more, more preferably 2 MPa or more, and the upper limit is preferably 7 MPa or less, from the viewpoint of achieving excellent low temperature fluidity and energy efficiency of the isomerization treatment, etc. More preferably, it is 5 MPa or less. The reaction temperature is preferably 200 ° C. or more, more preferably 250 ° C. or more, and the upper limit is preferably 460 ° C. or less, more preferably 360 ° C. or less.

From the same viewpoint as this, the liquid hourly space velocity (LHSV) is preferably 0.2 hr- ¹ or more, more preferably 0.3 hr- ¹ or more, and preferably 3.0 hr- ¹ or less as the upper limit. Preferably it is 2.0 hr < ^-1 > or less. The hydrogen / The oil ratio, preferably 150 Nm ³ / kL or more, more preferably 500 Nm ³ / kL or more, still more preferably from 900 Nm ³ / kL or more, preferably not more than 1500 Nm ³ / kL upper limit, more preferably It is at most 1300 Nm ³ / kL, more preferably at most 1100 Nm ³ / kL.

  In fuel base A obtained by subjecting raw materials containing animal and vegetable fats and / or components derived from animal and vegetable fats and oils through hydrodeoxygenation treatment and isomerization treatment, the content of isomers (isoparaffins) in all fatty acid derivatives is preferably It is 40 mol% or more, more preferably 45 mol% or more, and still more preferably 50 mol% or more. When the content of the isomer is in the above range, better low temperature fluidity can be obtained, and the specification of light oil can be easily satisfied. In the present specification, the content of the isomer is a gas chromatograph / hydrogen flame ionization type detector (nonpolar column: capillary column: DB-1 MS (manufactured by Agilent Technologies)), carrier gas (He) flow rate 2.0 mL / Min column temperature: 50 ° C to 340 ° C at 5 ° C / min, sample injection temperature: 360 ° C, detector temperature: 360 ° C It is.

<Properties of Fuel Base Material A>
As the properties of the fuel base A, the cetane index is preferably 70 or more, more preferably from the viewpoint of obtaining a higher cetane index and better low temperature fluidity, and from the viewpoint of easily satisfying the specification of light oil. It is 80 or more, more preferably 90 or more. In the present specification, cetane index is a method of calculating cetane index using a four-variable equation defined in JIS K 2280-5 (Petroleum products-Determination of octane number, cetane number and cetane index-part 5: cetane index) Measured according to the

  The pour point of the fuel base A is preferably 3 ° C. or less, more preferably 2 ° C. or less, still more preferably 1 ° C. or less. The lower limit is not particularly limited, but is usually −15 ° C. or more. In the present specification, the pour point is a value measured in accordance with the pour point test method defined in JIS K 2269 (Pour point of crude oil and petroleum products and cloud point test method of petroleum products).

  The clogging point of the fuel base A is preferably 3 ° C. or less, more preferably 2 ° C. or less, still more preferably 1 ° C. or less. The lower limit is not particularly limited, but is usually −10 ° C. or more. In the present specification, the clogging point is a cryogenic filter clogging point (CFPP) measured according to the clogging point test method defined in JIS K 2288 (petroleum product-light oil-clogging point test method). .

Density at 15 ℃ of fuel base material A is preferably 0.70 g / cm ³ or more, more preferably 0.73 g / cm ³ or more, more preferably 0.75 g / cm ³ or more, preferably the upper limit 0 .90g / cm ³ or less, more preferably 0.87 g / cm ³ or less, further preferably 0.85 g / cm ³ or less. In the present specification, the density at 15 ° C. is a value measured in accordance with JIS K 2249 (Density test method for crude oil and petroleum products and density / mass / volume conversion table).

The kinematic viscosity of the fuel base A at 30 ° C. is preferably 2.5 mm ² / s or more, more preferably 3.0 mm ² / s or more, and still more preferably 3.5 mm ² / s or more. 5.0 mm ² / s or less, more preferably 4.7 mm ² / s, more preferably not more than 4.5 mm ² / s. In the present specification, the kinematic viscosity at 30 ° C. is a value measured in accordance with JIS K 2283 (Crude oil and petroleum products-kinetic viscosity test method and viscosity index calculation method).

  As a distillation temperature of fuel base material A, 50 volume% distillation temperature (T50) is preferably 250 ° C. or more and 320 ° C. or less, and 90 volume% distillation temperature (T90) is preferably 260 ° C. or more and 340 ° C. or less . The distillation temperature in the present specification is a distillation temperature measured by a distillation test in accordance with JIS K 2254 (petroleum product-distillation test method).

  The flash point of the fuel base A is preferably 90 ° C. or more, more preferably 100 ° C. or more, and still more preferably 110 ° C. or more. In the present specification, the flash point is a value measured by JIS K 2265-3 (how to obtain the flash point-Part 3: Pensky-Marten sealing method).

  The sulfur content of the fuel base A is preferably as low as possible, and specifically preferably 3 ppm by mass or less, more preferably 2 ppm by mass or less, and further preferably 1 ppm by mass or less. In the present specification, the sulfur content is a value measured in accordance with JIS K 2541-6 (Petroleum and petroleum products-Sulfur content test method-Part 6: Ultraviolet fluorescence method).

  The aroma content of the fuel base A is preferably 0.3% by volume or less, more preferably 0.1% by volume or less. In the present specification, the aroma content is a value measured in accordance with JPI-5S-49-2007 (petroleum product-hydrocarbon type test method-high performance liquid chromatography method).

(Fuel base material B)
The fuel base material B is obtained by hydrotreating a mixed gas oil of straight-run light oil (base material X) and cracked light oil (base material Y).
<Straight-run light oil (base material X)>
The straight-run light oil (base material X) used in the present embodiment is a light oil obtained from an atmospheric distillation apparatus of crude oil.
As the properties of straight-run light oil (base material X), the cetane index of straight-run light oil is, from the viewpoint of obtaining a higher cetane index and better low-temperature fluidity, and from the viewpoint of easily satisfying the specification of light oil, Preferably it is 50 or more, More preferably, it is 55 or more.
The pour point of straight-run light oil (base material X) is preferably 0 ° C. or less, more preferably −2.5 ° C. or less, still more preferably −5.0 ° C. or less, and the lower limit is not particularly limited, It is usually -10.0 ° C or more.
The clogging point of straight-run light oil (base material X) is preferably 2 ° C. or less, more preferably 0 ° C. or less, still more preferably −2 ° C. or less, and the lower limit is not particularly limited, but is usually −5 ° C. It is above.

The density at 15 ° C. of straight-run light oil (base material X) is preferably 0.800 g / cm ³ or more, more preferably 0.810 g / cm ³ or more, still more preferably 0.815 g / cm ³ or more, and the upper limit as preferably 0.900 g / cm ³ or less, more preferably 0.880 g / cm ³ or less, more preferably 0.860 g / cm ³ or less.
Kinematic viscosity at 30 ° C. of straight run gas oil (base X) is preferably 2.5 mm ² / s or more, more preferably 2.7 mm ² / s or more, more preferably 3.0 mm ² / s or more, The upper limit is preferably 6.5 mm ² / s or less, more preferably 6.0 mm ² / s or less, and still more preferably 5.5 mm ² / s or less.

As distillation temperature of straight distillation light oil (base material X), 50% by volume distillation temperature (T50) is preferably 250 ° C or more and 320 ° C or less, 90% by volume distillation temperature (T90) is preferably 290 ° C or more 375 It is less than ° C.
The flash point of the straight-run light oil (base material X) is preferably 45 ° C. or more, more preferably 50 ° C. or more, still more preferably 55 ° C. or more.

The sulfur content of the straight-run light oil (base material X) is preferably as low as possible, and specifically preferably 2.0% by mass or less, more preferably 1.6% by mass or less, and still more preferably 1.2% by mass or less .
The aroma fraction of the straight-run light oil (base material X) is preferably 35% by volume or less, more preferably 30 or less, and the lower limit is usually 20% by volume or more.

<Decomposed light oil (base Y)>
Examples of the cracked gas oil used in the present invention include a catalytic cracker, a gas oil fraction (LCO) obtained from a residual oil catalytic cracker, and a cracked gas oil (DSGO) obtained from a heavy oil desulfurizer. Specifically, for example, heavy gas oil as a raw material oil, vacuum gas oil, and a mixed oil thereof are subjected to hydrodesulfurization using a vacuum gas oil desulfurization apparatus, and then indirect distillation is obtained by fractionating in a distillation column. The light oil etc. which are obtained by carrying out catalytic decomposition of heavy gas oil with a catalytic cracking device are mentioned.
Also, as the cracked gas oil (base Y), not only the catalytic cracked light oil by-produced from the catalytic cracking unit but also, for example, refined catalytic cracking in which the content of impurities such as sulfur content is reduced by further hydrorefining It is also possible to use light cracked light oil (boiling point: fraction of 170 ° C. or more and 280 ° C. or less) after distillation of light oil and catalytically cracked light oil and fractionation into light and heavy fractions.

As the properties of cracked gas oil (base Y), the cetane index of cracked gas oil is preferably from the viewpoint of obtaining higher cetane index and better low temperature fluidity, and from the viewpoint of easily satisfying the specifications of gas oil. It is 15 or more, more preferably 18 or more, further preferably 20 or more.
The pour point of the cracked gas oil (base Y) is preferably -5 ° C or less, more preferably -7 ° C or less, still more preferably -10 ° C or less, and the lower limit is not particularly limited, but usually -40 ° C It is above.
The clogging point of the cracked gas oil (base Y) is preferably -3 ° C or less, more preferably -5 ° C or less, still more preferably -8 ° C or less, and the lower limit is not particularly limited, but is usually -30 ° C or more.

Density at 15 ℃ of cracked gas oil (base Y) is preferably 0.850 g / cm ³ or more, more preferably 0.870 g / cm ³ or more, upper limit is preferably 0.990 g / cm ³ or less, more Preferably it is 0.970 g / cm < ³ > or less.
As distillation temperature of cracked light oil (base material Y), 10 volume% distillation temperature (T10) is preferably 180 ° C or more and 240 ° C or less, 50 volume% distillation temperature (T50) is preferably 250 ° C or more and 300 ° C Hereinafter, the 90 vol% distillation temperature (T90) is preferably 310 ° C. or more and 380 ° C. or less.
The flash point of the cracked gas oil (base Y) is preferably 45 ° C. or more, more preferably 50 ° C. or more, still more preferably 55 ° C. or more.

The sulfur content of the cracked gas oil (base Y) is preferably as low as possible, specifically preferably 0.7% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0.3% by mass or less .
The aroma content of the cracked light oil (base Y) is preferably 85% by volume or less, more preferably 80% by volume or less, and the lower limit is usually 35% by volume or more.

<Mixed light oil>
The content of the cracked gas oil in the mixed gas oil of straight-run gas oil (base material X) and cracked gas oil (base material Y) is preferably 2% by volume or more, more preferably 5% by volume or more, still more preferably 10% by volume The upper limit is preferably 30% by volume or less, more preferably 25% by volume or less, and still more preferably 23% by volume or less. When the content of the cracked gas oil is in the above range, a higher cetane index and better low temperature fluidity can be easily obtained, and the specifications of the gas oil can be easily satisfied.

<Hydrogenation of mixed gas oil>
The fuel base material B is obtained by hydrotreating the mixed light oil of the straight-run light oil (base material X) and the cracked light oil (base material Y) described above.
The hydrogenation treatment is preferably carried out, for example, on a metal oxide support such as preferably alumina or titania, preferably a Group 6, and a Group 8 to 10 metal element, more preferably molybdenum, tungsten, cobalt, nickel etc. More preferably, it is carried out in the presence of a catalyst supporting an active metal such as molybdenum, cobalt, nickel and the like. Here, as the active metal, the above metals can be used singly or in combination of two or more kinds, and the supported amount of molybdenum, cobalt and nickel is preferably 2% by mass to 30% by mass and 1% by mass to 10%. It is about 1% by mass or more and 10% by mass or less.
The hydrotreating is performed in the presence of the above catalyst, for example, under the following conditions.
The hydrogen partial pressure is preferably 2 MPa or more and 13 MPa or less, more preferably 3 MPa or more and 12 MPa or less, and still more preferably 4 MPa or more and 11 MPa or less. The temperature condition is preferably 300 ° C. or more and 400 ° C. or less, more preferably 310 ° C. or more and 390 ° C. or less.
The liquid hourly space velocity (LHSV), preferably 0.2 hr ^-1 or more 3.0 hr ^-1 or less, more preferably 0.3 hr ^-1 or more 1.5hr ^-1 or less, more preferably 0.4Hr ^-1 or 1 .2 hr ^-1 or less.
Further, as the hydrogen / mixing gas oil ratio, from the viewpoint of preventing deterioration of the catalyst, preferably 180 Nm ³ / kL or more, more preferably 200 Nm ³ / kL or more, further preferably 240 nm ³ / kL or more. From the viewpoint of the effect as, preferably not more than 500 Nm ³ / kL, more preferably 400 Nm ³ / kL or less, more preferably 300 Nm ³ / kL or less.

<Properties of Fuel Base Material B>
As the properties of the fuel base material B, the cetane index is preferably 40 or more, more preferably from the viewpoint of obtaining higher cetane index and better low temperature fluidity, and in terms of easily satisfying the specification of light oil. It is 45 or more, more preferably 50 or more.
The pour point of the fuel base B is preferably 0 ° C. or less, more preferably −2.5 ° C. or less, still more preferably −5 ° C. or less, and the lower limit is not particularly limited, but usually −10 ° C. or more is there.
The clogging point of the fuel base B is preferably 2 ° C. or less, more preferably 0 ° C. or less, still more preferably −2 ° C. or less. The lower limit is not particularly limited, but is usually −5 ° C. or more.

The density of the fuel base B at 15 ° C. is preferably 0.800 g / cm ³ or more, more preferably 0.810 g / cm ³ or more, still more preferably 0.820 g / cm ³ or more, and the upper limit is preferably 0. .900g / cm ³ or less, more preferably 0.880 g / cm ³ or less, more preferably 0.860 g / cm ³ or less.
Kinematic viscosity at 30 ° C. of the fuel base material B is preferably 2.5 mm ² / s or more, more preferably 2.8 mm ² / s or more, further preferably 3.0 mm ² / s or more, preferably the upper limit is It is 6.0 mm ² / s or less, more preferably 4.5 mm ² / s or less, still more preferably 4.0 mm ² / s or less.

As a distillation temperature of the fuel base B, 10 vol% distillation temperature (T10) is preferably 160 ° C. or more and 230 ° C. or less, and 50 vol% distillation temperature (T50) is preferably 240 ° C. or more and 320 ° C or less, 90 The volume% distillation temperature (T90) is preferably 300 ° C. or more and 370 ° C. or less.
The flash point of the fuel base B is preferably 45 ° C. or more, more preferably 50 ° C. or more, still more preferably 55 ° C. or more.

The sulfur content of the fuel base B is preferably as low as possible, and specifically preferably 15 ppm by mass or less, more preferably 10 ppm by mass or less, and further preferably 8 ppm by mass or less.
The aroma content of the fuel base B is preferably 40% by volume or less, more preferably 35% by volume or less, and the lower limit is usually 20% by volume or more. If the content of the aroma is within the above range, better low temperature fluidity can be obtained.

(Diesel fuel composition)
The diesel fuel composition of the present embodiment contains the fuel base A and the fuel base B. Fuel base A has the advantage that it has a high cetane index, but it has the properties of high pour point, high clogging point and insufficient low temperature fluidity, and fuel base B has high flow point, clogging point The base material has the property of having a relatively low cetane index although it has the advantage of having a low low temperature fluidity and an excellent low temperature fluidity. The diesel fuel composition of the present embodiment compensates for each other's defects by the advantages of these fuel bases A and B, and has a high cetane index and excellent cold flowability.

  In the diesel fuel composition of the present embodiment, the content based on the total amount of the fuel base A is preferably 5% by volume or more, more preferably 10% by volume or more, still more preferably 15% by volume or more, particularly preferably The upper limit thereof is preferably 60% by volume or less, more preferably 55% by volume or less, and still more preferably 50% by volume or less. If the content of the fuel base A is in the above range, a higher cetane index and better low temperature fluidity can be obtained, and the specification of light oil can be easily satisfied.

  In the diesel fuel composition of the present embodiment, the content based on the total amount of the fuel base B is preferably 10% by volume or more, more preferably 20% by volume or more, still more preferably 30% by volume or more, particularly preferably The upper limit thereof is preferably 95% by volume or less, more preferably 90% by volume or less, still more preferably 85% by volume or less, and particularly preferably 75% by volume or less. If the content of the fuel base B is in the above range, a higher cetane index and better low temperature fluidity can be obtained, and the specification of light oil can be easily satisfied.

The diesel fuel composition of the present embodiment may further contain a product light oil and a desulfurized straight-run light oil (fuel base C) (also referred to as DGO) obtained by hydrotreating a straight-run light oil (base material X). Here, the properties of the desulfurized straight-run light oil (fuel base C) are the same as the properties of the straight-run light oil (base X) except for the sulfur content. The sulfur content of the desulfurized directly distilled gas oil (fuel base C) is usually 15 mass ppm or less, 10 mass ppm or less, and 8 mass ppm or less.
In the diesel fuel composition, the content based on the total amount of the composition of the desulfurized straight-run light oil (fuel base C) is preferably 1% by volume or more, more preferably 5% by volume or more, still more preferably 10% by volume or more The upper limit is preferably 65% by volume or less, more preferably 60% by volume or less, and still more preferably 50% by volume or less. When the content of straight-run light oil is in the above range, a higher cetane index can be obtained, and the specification of light oil can be easily satisfied.

  The diesel fuel composition of the present embodiment is at least one selected from desulfurized kerosene (DK), hydrocracked gas oil (HCGO), and hydrocracked kerosene (HCK), as long as the effects of the invention are not impaired. May be included.

Further, the diesel fuel composition of the present embodiment is an additive generally used for the fuel composition, for example, a cetane number improver such as a nitrate ester, an organic peroxide, etc., as long as the effects of the invention are not impaired. Lubricity improvers such as carboxylic acids such as acid, oleic acid and stearic acid, esters of the carboxylic acids and alkyl alcohol; detergents such as alkenyl succinimide; ethylene co-weight such as ethylene-vinyl acetate copolymer Low-temperature flow improvers such as combination, vinyl esters of saturated fatty acids such as vinyl acetate, vinyl propionate and vinyl butyrate, alkenylsuccinic acid amides; antioxidants such as amines and phenols; additives such as antistatic agents May be included.
Among these additives, it is preferable to use a low temperature fluidity improver, since both the pour point and clogging point of the diesel fuel composition are lowered and improvement in low temperature fluidity is expected.
When a low temperature fluidity improver is used, the content based on the total amount of the composition is preferably 10 mass ppm or more, more preferably 100 mass ppm or more, still more preferably 250 mass ppm or more, preferably as an upper limit Is 800 ppm by mass or less, more preferably 700 ppm by mass or less, still more preferably 500 ppm by mass or less. When the content of the low temperature fluidity improver is in the above range, an excellent improvement effect on low temperature fluidity can be obtained.

<Properties of diesel fuel composition>
As a property of the diesel fuel composition of the present embodiment, the cetane index is preferably 50 or more, more preferably 53 or more, still more preferably 55 or more, and particularly preferably 58 or more.
The pour point of the diesel fuel composition of this embodiment is preferably -15 ° C or less, more preferably -16 ° C or less, still more preferably -17 ° C or less, particularly preferably -20 ° C or less, and the lower limit is particularly preferably Although there is no limitation, it is usually -25 ° C or higher.
The clogging point of the diesel fuel composition of the present embodiment is preferably −5 ° C. or less, more preferably −8 ° C. or less, and still more preferably −12 ° C. or less, and the lower limit is not particularly limited. 20 ° C. or higher.
The diesel fuel composition of the present embodiment has excellent low temperature fluidity because both the pour point and the clogging point are low. For example, even if the pour point is low, if the clogging point is high, when trying to start the diesel engine in a low temperature environment, the filters attached to the fuel injection pump and the fuel supply pump are blocked by wax and the engine stops There is a risk of Thus, in order to obtain excellent low temperature fluidity, it is important that the pour point and the clogging point are both low.

The density at 15 ° C. of the diesel fuel composition of the present embodiment is preferably 0.800 g / cm ³ or more, more preferably 0.810 g / cm ³ or more, still more preferably 0.815 g / cm ³ or more, and the upper limit as preferably 0.860 g / cm ³ or less, more preferably 0.850 g / cm ³ or less, more preferably 0.840 g / cm ³ or less.
Kinematic viscosity at 30 ° C. of the diesel fuel composition of the present embodiment is preferably 2.7 mm ² / s or more, more preferably 2.8 mm ² / s or more, more preferably 3.0 mm ² / s or more, preferably 4.5 mm ² / s or less as the upper limit, more preferably 4.3 mm ² / s, more preferably not more than 4.0 mm ² / s.

The distillation temperature of the diesel fuel composition of the present embodiment is preferably 50% by volume distillation temperature (T50) of 260 ° C. or more and 320 ° C. or less, and 90% by volume distillation temperature (T90) is preferably 290 ° C. or more It is less than ° C.
The flash point of the diesel fuel composition of the present embodiment is preferably 45 ° C. or more, more preferably 50 ° C. or more, still more preferably 55 ° C. or more.

The sulfur content of the diesel fuel composition of the present embodiment is preferably as low as possible, specifically preferably 10 ppm by mass or less, more preferably 8 ppm by mass or less, and still more preferably 6 ppm by mass or less.
The aroma content of the diesel fuel composition of the present embodiment is preferably 30% by volume or less, more preferably 28% by volume or less, and the lower limit is usually 5% by volume or more.

  Thus, the diesel fuel composition of the present embodiment is a fuel composition containing biomass fuel having a high cetane index and excellent low temperature fluidity, and also JIS No. 1 light oil, JIS No. 1 light oil, JIS No. 2 It is a composition that can meet the specifications of light oil such as light oil.

[Method of producing diesel fuel composition]
The diesel fuel composition according to the present embodiment is, for example, a step of preparing fuel base A by hydrodeoxygenating and isomerizing a raw material containing animal and vegetable fats and / or components derived from animal and vegetable fats and oils. A step of preparing a fuel base B by subjecting a mixed light oil obtained by mixing a distillate light oil (base X) and a cracked light oil (base Y) to a hydrogenation treatment, and mixing the fuel base A and the fuel base B It can obtain by the manufacturing method which includes a process in order. According to this manufacturing method, it is possible to obtain the diesel fuel composition according to the present embodiment, which has a high cetane index and excellent low temperature fluidity.

Raw materials containing animal and vegetable fats and / or ingredients derived from animal and vegetable fats and oils, hydrodeoxygenation treatment and isomerization treatment of this (the explanation for preparing fuel base A) The description is the same as the description given for the fuel base A in the diesel fuel composition of the embodiment, and thus the description is omitted. Further, the fuel base material B is also the same as the description given for the fuel base material B in the diesel fuel composition of the present embodiment described above, and thus the description thereof is omitted.
It should be noted that even before the step of hydrodeoxygenating the raw material containing animal and vegetable fats and / or ingredients derived from animal and vegetable fats and oils, a step of removing impurities such as alkali metals, alkaline earth metals and chlorine from the raw material is also included. Good. These impurities may become catalyst poisons in hydrodeoxygenation and may corrode the reactor in which hydrodeoxygenation is performed. Therefore, it is preferable to remove these impurities from the raw material before the hydrodeoxygenation treatment.
Methods of removing these impurities from the raw materials include column purification using polar columns such as silica, application of degumming-deoxidation-decoloring-deodoring used as a method of refining edible oil, and the like. For degumming-deacidifying-decolorizing-deodorizing, all four steps may be selected or only some of them may be selected. For example, only two or three steps such as degumming-decoloring, degumming-deacidifying-decoloring are effective in removing impurities.

  Further, the method for producing a diesel fuel composition described above further comprises the step of adding desulfurized straight-run light oil (fuel base C) and mixing as well when mixing fuel base A and fuel base B, and desulfurized kerosene (DK) And 4.) at least one selected from hydrocracked gas oil (HCGO) and hydrocracked kerosene (HCK) may be added and mixed.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.

[Evaluation method]

(Preparation of Fuel Base Material A)
Hydrodeoxygenation catalyst preparation
The catalyst was prepared with reference to JP 2010-235944. First, a titanium-containing aqueous solution was prepared based on WO 2002/049963 pamphlet. 12.7 g of hydrous titanium oxide powder and 70 g of pure water containing 85 mass% of titanium oxide (IV) (TiO ₂ ) content determined by firing at 500 ° C. for 4 hours in a glass beaker with an internal volume of 1 L The slurry was put in and stirred. Next, an aqueous solution prepared by mixing 78.7 g of 35 mass% hydrogen peroxide water and 26.5 g of 26 mass% ammonia water was added to the hydrous titanium oxide slurry. Then, it stirred for 3 hours, maintaining 25 degreeC, and obtained yellow-green and transparent titanium containing aqueous solution. Thereto, 28.4 g of citric acid first hydrate was added. Then, after hold | maintaining at the temperature of 30 degrees C or less for 6 hours, 120 g of transparent titanium containing aqueous solutions were obtained by pH 6.2 by holding at 80-95 degrees C for 12 hours. 58.5 g of the obtained titanium-containing aqueous solution was taken, diluted with pure water to make 80 mL, and impregnated with 100 μl of 4-leaf γ-alumina at a pore volume of 0.8 mL / g under normal pressure (pore filling method). Then, under reduced pressure using a rotary evaporator, after drying for 1 hour at 70 ° C., then dried for 3 hours at 120 ° C., finally calcined for 4 hours at 500 ° C., to obtain a _TiO 2 -5 wt% on an alumina support.

Next, 75.3 g (44.0 g as NiO) of basic nickel carbonate in which the proportion of nickel oxide (NiO) determined by firing at 500 ° C. for 4 hours is 58.4% by mass (molybdenum trioxide 220 g, positive) 250 mL of pure water is added to 34.5 g of phosphoric acid (29.3 g as P ₂ O ₅ ), dissolved at 80 ° C. with stirring, cooled at room temperature, and made constant volume to 264 mL with pure water An impregnating solution was prepared. 60 mL of the impregnating solution is collected, 6 g of triethylene glycol is added, diluted with pure water so as to meet the water absorption of 100 g of the TiO ₂ -5 mass% supported alumina carrier, and the pressure is adjusted under normal pressure Impregnated. Next, after drying under reduced pressure using a rotary evaporator at 70 ° C. for 1 hour, heat treatment was carried out at 120 ° C. for 16 hours to prepare catalyst precursor A. The catalyst 57% by weight alumina in the charged amount in terms, TiO ₂ is 3 mass%, NiO is 6 mass%, MoO ₃ 30 _mass%, P 2 _{O 5} was 4% by weight.

<Preparation of Isomerization Catalyst>
Ion-exchanged water is added to 19.9 mL of a dinitrodiammine platinum nitrate solution (50 g Pt / L, manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.) to prepare 62.9 g of a dinitrodiammine platinum nitrate aqueous solution (platinum impregnation solution), and this is a silica alumina 98.4 g of a carrier (N632HN (product number), pellet, manufactured by JGC Catalysts & Chemicals Co., Ltd.) was impregnated at normal pressure. Next, after drying for 20 minutes under vacuum conditions at 30 ° C. using a rotary evaporator, and further drying for 2 hours at 70 ° C., using a calcining furnace, heating for 10 hours at 120 ° C., then 400 ° C. The catalyst was calcined for 3 hours to prepare a silica alumina catalyst supporting 1 mass% platinum in terms of the preparation amount.

Pretreatment of raw material oil
Jatropha oil (manufactured by Nippon Vegetable Fuel Co., Ltd.) was used which was degummed and deacidified to remove Jatropha crude oil obtained by squeezing seeds such as crushed seed shell from oil obtained by squeezing seeds of Jatropha.

Hydrodeoxygenation treatment
In the fixed bed flow reactor, 10 cc of the above-mentioned hydrodeoxygenation catalyst was charged, and reduction treatment was performed at 375 ° C. for 18 hours in a hydrogen stream. Thereafter, hydrodeoxygenation of Jatropha oil was performed under the conditions of a reaction temperature of 375 ° C., a liquid hourly space velocity (LHSV) of 0.5 hr ⁻¹ , a hydrogen / oil ratio of 2000 Nm ³ / kL, and a pressure of 6 MPa. Then, the reaction was continued for about 500 hours to obtain a hydrodeoxygenated Jatropha oil.

<Isomerization treatment>
The fixed bed flow type reactor was charged with 10 cc of the above isomerization catalyst, and reduction treatment was performed at 380 ° C. for 18 hours in a hydrogen stream. Thereafter, the isomerization treatment of hydrodeoxygenated Jatropha oil is carried out under the conditions of a reaction temperature of 320 ° C., a liquid hourly space velocity (LHSV) of 1.0 hr ⁻¹ , a hydrogen / oil ratio of 1000 Nm ³ / kL and a pressure of 3 MPa. went. Then, the reaction was continued for about 250 hours to obtain 2 L of fuel base A (isomerized jatropha oil). The properties of the obtained fuel base material A are shown in Table 1.

(Fuel base material B)
Cobalt-molybdenum is a mixed light oil obtained by mixing 80% by volume and 20% by volume of straight-run light oil (fuel base X) and cracked light oil (fuel base Y) each having the properties shown in Table 1 The fuel base B was obtained by hydrogenation in the presence of a catalyst (carrier alumina; cobalt content 6% by mass; molybdenum content 25% by mass). The conditions for the hydrogenation treatment were such that the sulfur content contained in the fuel base B would be 0.0006 mass% (6 mass ppm). The properties of the obtained fuel base B are shown in Table 1.

(Fuel base material C)
Table 1 shows properties of the fuel base C (desulfurized straight distilled gas oil; DGO) used in the present example.

(Examples 1 to 3, Comparative Example 1)
The fuel base A, fuel base B, and fuel base C are mixed according to the composition shown in Table 2, and a low temperature fluidity improver ("Infineum R240", manufactured by Infineum Japan Co., Ltd.) is further added 400 The mass ppm was added to obtain the fuel composition of each example and comparative example. The cetane index, pour point, clogging point, and other properties were measured for the obtained fuel composition. The measurement results are shown in Table 2.

The diesel fuel compositions of Examples 1 to 3 have a cetane index of 58.5 to 65.4, a pour point of -22.5 to -20.0 ° C, and a clogging point of -15.0 to -14. 0 ° C., high cetane index, low pour point and low clogging point, and excellent cold flowability. On the other hand, the fuel composition of Comparative Example 1, which does not contain the fuel base B, has a cetane index and a pour point equivalent to those of the diesel fuel compositions of Examples 1 to 3, but has a high clogging point and low temperature fluidity It was confirmed that was not enough.
According to the comparison between the fuel base A shown in Table 1 and the diesel fuel compositions of Examples 1 to 3, the clogging point of the fuel base A is as high as 0 ° C., and the low temperature fluidity is not sufficient. In the diesel fuel compositions of Examples 1 to 3, the clogging point is as low as -15.0 to -14.0 ° C., and it can be seen that the low temperature fluidity is improved.
Further, according to the comparison between the fuel base B shown in Table 1 and the diesel fuel compositions of Examples 1 to 3, the diesel fuel compositions of Examples 1 to 3 are the pour point of the fuel base B and It was confirmed that the cetane index improved while maintaining the clogging point.

Claims (7)

  Fuel base A obtained by hydrodeoxygenating and isomerizing raw materials containing animal and vegetable fats and / or components derived from animal and vegetable fats and oils, and fuel base obtained by hydrotreating a mixed gas oil of straight run gas oil and cracked gas oil A diesel fuel composition containing B.   The diesel fuel composition according to claim 1, further comprising desulfurized straight distilled gas oil.   The diesel fuel composition according to claim 1, further comprising a low temperature fluidity improver.   The diesel fuel composition according to any one of claims 1 to 3, wherein a content based on the total amount of the composition of the fuel base A is 5% by volume or more and 60% by volume or less.   The diesel fuel composition according to any one of claims 1 to 4, wherein a content based on the total amount of the composition of the fuel base B is 10% by volume or more and 95% by volume or less.   The diesel fuel composition according to any one of claims 2 to 5, wherein a content based on the total amount of the composition of the desulfurized straight-run light oil is 1% by volume or more and 65% by volume or less.   The diesel fuel composition according to any one of claims 1 to 6, wherein the cetane index is 50 or more, the pour point is -15 ° C or less, and the clogging point is -5 ° C or less.