JP5639531B2 - Gasoline composition and method for producing the same - Google Patents

Description

  The present invention relates to a gasoline composition useful as a fuel for automobiles and a method for producing the same.

For gasoline, naphtha fraction obtained by atmospheric distillation of crude oil, catalytic cracked gasoline by catalytic cracking method, alkylate obtained by alkylation, reformed gasoline obtained by catalytic reforming method, aroma from reformed gasoline Various base materials, such as raffinate which is the residue which extracted the group, and isoolefin, are used (for example, refer patent documents 1 and 2). In order to produce the optimum automotive fuel, it is necessary to blend these substrates well.
On the other hand, current automobile-related problems include deterioration of performance due to deposits accumulated in the engine and environmental problems such as reduction of carbon dioxide and regulated exhaust gas. In particular, deposits in the combustion chamber of a gasoline engine can cause deterioration of power performance, fuel consumption, exhaust gas, and carbon knock due to disturbance of the combustion state of the engine.
Examination of the relationship between fuel properties and combustion chamber deposits has pointed out that when conventional reformate gasoline is blended, the deposits in the combustion chamber are significantly increased (see Non-Patent Document 1, for example). If the amount of reformed gasoline in the product gasoline can be reduced, the combustion chamber deposit may be reduced.

JP-T-2004-507576 Special table 2003-523453 gazette

Peter J. Choate et al., Relationship Between Combustion Chamber Deposit, Fuel Compositon, and Combution Cham, ber Deposit Structure, SAE Paper 932812, 1993

However, the reformed gasoline base material is a main base material for achieving a high octane number, and the reduction causes a decrease in the octane number. Moreover, there is a risk of causing deterioration in fuel consumption due to a decrease in density and a change in distillation properties of gasoline. In particular, when the octane number decreases, the engine may be damaged due to knocking, and the engine performance may not be maximized in a premium gasoline specification vehicle. Further, if the distillation property of gasoline changes greatly, there is a risk that the drivability and acceleration of the vehicle will deteriorate.
The present invention has been made in view of such circumstances, and a method for producing a gasoline composition having a low combustion gas deposit generation ability and low exhaust gas (NOx) performance while maintaining an octane number and distillation properties. The purpose is to provide.

As a result of intensive studies on the above problems, the inventors of the present invention have found that in a method for producing a gasoline composition, a cracked and reformed gasoline base material, a catalytic cracked gasoline base material, and a hydrocarbon base material having 4 carbon atoms having predetermined properties. It is found that by adding a predetermined amount of the fuel, the combustion chamber deposit can be reduced, the engine performance can be maximized, and further, high-performance gasoline with less carbon dioxide emission can be obtained, and the present invention has been completed. It came to do.
That is, the present invention is as follows.

[1] A cracked and reformed gasoline base material having the following properties (1) to (7) 1 to 35% by volume, a catalytic cracked gasoline base material 10 to 90% by volume, and a hydrocarbon base 4 having 4 carbon atoms. A method for producing a gasoline composition having a research octane number of 89 or more and less than 96, wherein at least 1 to 10% by volume is blended.
(1) 90% by volume or more of aromatic content (2) 5% by volume or less of olefin content (3) 5 to 50% by volume of aromatics having 8 carbon atoms
(4) Aromatic content of 9 or more carbon atoms is 30% by volume or less (5) Sulfur content is 20 mass ppm or less (6) Research octane number is 110 or more (7) Density at 15 ° C. is 0.8 to 0.95 g / cm ³

[2] The method for producing gasoline according to [1], wherein the cracked and reformed gasoline base material is blended so as to satisfy 0.10 ≦ A / B ≦ 1.0.
(A represents the content (volume%) of the aromatic component derived from the cracked and reformed gasoline base material, and B represents the content (volume%) of the total aromatic content in the gasoline composition.)

[3] The method for producing a gasoline composition according to [1] or [2], wherein the gasoline composition satisfies the following (1) to (7).
(1) Density at 15 ° C. is 0.783 g / cm ³ or less (2) Sulfur content is 10 mass ppm or less (3) Total aromatic content is 35% by volume or less (4) Benzene is 1% by volume or less (5) Olefin 30% by volume or less (6) 10% by volume distillation temperature is 70 ° C. or less, 50% by volume distillation temperature is 110 ° C. or less, and 90% by volume distillation temperature is 180 ° C. or less. (7) Distillation temperature 70 Distillation volume at 70 ℃ (E70) is 40% or less

[4] The cracked and reformed gasoline base material contains medium pore zeolite and / or large pore zeolite containing 10% by volume distillation temperature of 140 ° C. or more and 90% by volume distillation temperature of 380 ° C. or less. It is produced by performing a cracking and reforming reaction with a reaction temperature of 400 to 650 ° C., a reaction pressure of 1.5 MPaG or less, and a contact time of 1 to 300 seconds. The method for producing a gasoline composition according to any one of [1] to [3].

[5] A gasoline composition obtained by the method for producing a gasoline composition according to any one of [1] to [4].

  By the method of the present invention, it is possible to produce a gasoline composition capable of reducing the combustion chamber deposit and reducing the discharged carbon dioxide while maintaining the octane number and the distillation properties.

The present invention is described in detail below.
The method for producing the gasoline composition of the present invention comprises a cracked and reformed gasoline base material having a predetermined property of 1 to 35% by volume, a catalytic cracked gasoline base material of 10 to 90% by volume, and a hydrocarbon base material having 4 carbon atoms. It is characterized by blending 0.1 to 10% by volume.

In the method for producing a gasoline composition according to the present invention, the cracked and reformed gasoline base is blended in an amount of 1 to 35% by volume based on the total amount of the gasoline composition. From the viewpoint of improving the octane number and reducing carbon dioxide emissions, the cracked and reformed gasoline base material is preferably 3% by volume or more, more preferably 5% by volume or more, and further preferably 15% by volume or more. On the other hand, from the viewpoint of maintaining evaporation characteristics, it is preferably 35% by volume or less.
Furthermore, the ratio (A / B) of the aromatic content A (volume%) derived from the cracked and reformed gasoline base to the total aromatic content B (volume%) in the gasoline composition is 0 in terms of suppressing increase in combustion chamber deposits. It is preferable to mix | blend so that it may become 1 or more and 1.0 or less.

The cracked and reformed gasoline base material according to the present invention contains medium-oil zeolite and / or large-pore zeolite in a feed oil having a 10% by volume distillation temperature of 140 ° C or higher and a 90% by volume distillation temperature of 380 ° C or lower. It is produced by performing a cracking and reforming reaction with a reaction temperature of 400 to 650 ° C., a reaction pressure of 1.5 MPaG or less, and a contact time of 1 to 300 seconds. .
Specifically, the cracking / reforming substrate used in the present invention is produced by fractional distillation from the cracking / reforming reaction product obtained by the following cracking / reforming reaction.

  In the cracking and reforming reaction, the feedstock oil is brought into contact with the catalyst for cracking and reforming reaction, and the saturated hydrocarbon contained in the feedstock oil is used as the hydrogen donor source. Partially hydrogenated, ring-opened to convert to monocyclic aromatic hydrocarbons, converted to monocyclic aromatic hydrocarbons by cyclizing and dehydrogenating saturated hydrocarbons obtained in feedstock or in the cracking process The fuel base material mainly containing aromatic hydrocarbons can be produced.

The feed oil for the cracking and reforming reaction is preferably an oil having a 10 vol% distillation temperature of 140 ° C or higher and a 90 vol% distillation temperature of 380 ° C or lower, and the 10 vol% distillation temperature of the raw oil is 150 ° C or higher. More preferably, the 90 vol% distillation temperature of the feedstock is more preferably 360 ° C or lower.
In addition, 10 volume% distillation temperature and 90 volume% distillation temperature here mean the value measured based on JISK2254 "petroleum product-distillation test method".
Examples of the feed oil having a 10% by volume distillation temperature of 140 ° C. or higher and a 90% by volume distillation temperature of 380 ° C. or lower include cracked light oil (LCO) produced by a fluid catalytic cracker, LCO hydrorefined oil, Examples include coal liquefied oil, heavy oil hydrocracked refined oil, straight-run kerosene, straight-run light oil, coker kerosene, coker light oil, and oil sand hydrocracked refined oil.

  Examples of the reaction format when the raw material oil is brought into contact with and reacted with the cracking reforming reaction catalyst include a fixed bed, a moving bed, and a fluidized bed. Among them, since the heavy component is used as a raw material, a fluidized bed capable of continuously removing the coke component adhering to the catalyst and performing the reaction stably is preferable, and the space between the reactor and the regenerator is preferable. A continuous regenerative fluidized bed is particularly preferred in which the catalyst circulates and the reaction-regeneration can be repeated continuously. The feedstock oil in contact with the cracking reforming reaction catalyst is preferably in a gas phase. Moreover, you may dilute a raw material with gas as needed.

The catalyst for the cracking reforming reaction contains crystalline aluminosilicate.
The crystalline aluminosilicate is preferably a medium pore zeolite and / or a large pore zeolite because the yield of monocyclic aromatic hydrocarbons can be further increased.
The medium pore zeolite is a zeolite having a 10-membered ring skeleton structure. Examples of the medium pore zeolite include AEL type, EUO type, FER type, HEU type, MEL type, MFI type, NES type, and TON type. And zeolite having a WEI type crystal structure. Among these, the MFI type is preferable because the yield of monocyclic aromatic hydrocarbons can be further increased.
The large pore zeolite is a zeolite having a 12-membered ring skeleton structure. Examples of the large pore zeolite include AFI type, ATO type, BEA type, CON type, FAU type, GME type, LTL type, and MOR type. , Zeolites of MTW type and OFF type crystal structures. Among these, BEA type, FAU type, and MOR type are preferable in terms of industrial use, and the BEA type is more preferable because the yield of monocyclic aromatic hydrocarbons can be further increased.

The crystalline aluminosilicate may contain, in addition to the medium pore zeolite and the large pore zeolite, a small pore zeolite having a skeleton structure having a 10-membered ring or less, and a very large pore zeolite having a skeleton structure having a 14-membered ring or more. Good.
Here, examples of the small pore zeolite include zeolites having crystal structures of ANA type, CHA type, ERI type, GIS type, KFI type, LTA type, NAT type, PAU type, and YUG type.
Examples of the ultra-large pore zeolite include zeolites having CLO type and VPI type crystal structures.

  When the cracking and reforming reaction is a fixed bed reaction, the content of crystalline aluminosilicate in the cracking and reforming reaction catalyst is 60 to 100% by weight when the entire catalyst for cracking and reforming reaction is 100% by weight. Preferably, 70-100 mass% is more preferable, and 90-100 mass% is especially preferable. If the content of the crystalline aluminosilicate is 60% by mass or more, the yield of monocyclic aromatic hydrocarbons can be sufficiently increased. When the cracking and reforming reaction is a fluidized bed reaction, the content of crystalline aluminosilicate in the cracking and reforming reaction catalyst is 20 to 60% by mass when the entire catalyst for cracking and reforming reaction is 100% by mass. Preferably, 30 to 60% by mass is more preferable, and 35 to 60% by mass is particularly preferable. If the content of the crystalline aluminosilicate is 20% by mass or more, the yield of monocyclic aromatic hydrocarbons can be sufficiently increased. When the content of the crystalline aluminosilicate exceeds 60% by mass, the content of the binder that can be blended with the catalyst is reduced, which may be unsuitable for fluidized beds.

  The cracking reforming reaction catalyst preferably contains phosphorus and / or boron. When the catalyst for cracking and reforming reaction contains phosphorus and / or boron, it is possible to prevent the yield of monocyclic aromatic hydrocarbons from decreasing with time and to suppress the formation of coke on the catalyst surface.

  Examples of the method for incorporating phosphorus into the cracking reforming reaction catalyst include an ion exchange method and an impregnation method. Specifically, a method in which phosphorus is supported on crystalline aluminosilicate, crystalline aluminogallosilicate, or crystalline aluminodine silicate, a phosphorus compound is included during zeolite synthesis, and a part of the crystalline aluminosilicate skeleton is added to phosphorus. Examples include a replacement method, a method using a crystal accelerator containing phosphorus during zeolite synthesis, and the like. The phosphate ion-containing aqueous solution used at that time is not particularly limited, but was prepared by dissolving phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, and other water-soluble phosphates in water at an arbitrary concentration. Can be preferably used.

  Examples of the method for incorporating boron into the cracking reforming reaction catalyst include an ion exchange method and an impregnation method. Specifically, a method in which boron is supported on crystalline aluminosilicate, crystalline aluminogallosilicate, or crystalline aluminosilicate, a boron compound is included during zeolite synthesis, and a part of the skeleton of crystalline aluminosilicate is combined with boron. Examples include a replacement method, a method using a crystal accelerator containing boron at the time of zeolite synthesis, and the like.

  The phosphorus and / or boron content in the catalyst for cracking and reforming reaction is preferably 0.1 to 10% by mass relative to the total weight of the catalyst, and more preferably the lower limit is 0.5% by mass or more. The upper limit is more preferably 9% by mass or less, and particularly preferably 8% by mass or less. When the content of phosphorus with respect to the total weight of the catalyst is 0.1% by mass or more, a decrease in the yield of monocyclic aromatic hydrocarbons over time can be prevented, and when the content is 10% by mass or less, the monocyclic aromatics The yield of hydrocarbons can be increased.

The cracking and reforming reaction catalyst may contain gallium and / or zinc as necessary. If gallium and / or zinc is contained, the production rate of monocyclic aromatic hydrocarbons can be increased.
The gallium-containing form in the catalyst for cracking and reforming reaction includes those in which gallium is incorporated in the lattice skeleton of crystalline aluminosilicate (crystalline aluminogallosilicate), and those in which gallium is supported on crystalline aluminosilicate (gallium) Supported crystalline aluminosilicate) and those containing both.
Zinc-containing forms in the catalyst for cracking and reforming reaction include those in which zinc is incorporated in the lattice skeleton of crystalline aluminosilicate (crystalline aluminodin silicate), and in which zinc is supported on crystalline aluminosilicate (zinc Supported crystalline aluminosilicate) and those containing both.

Crystalline aluminogallosilicate and crystalline aluminodine silicate have a structure in which SiO ₄ , AlO ₄ and GaO ₄ / ZnO ₄ structures are present in the skeleton. The crystalline aluminogallosilicate and the crystalline aluminodine silicate can be obtained by, for example, gel crystallization by hydrothermal synthesis, or a method of inserting gallium or zinc into the lattice skeleton of the crystalline aluminosilicate. Crystalline aluminogallosilicate and crystalline aluminozine silicate can be obtained by a method of inserting aluminum into the lattice skeleton of crystalline gallosilicate or crystalline zincosilicate.

The gallium-supporting crystalline aluminosilicate is obtained by supporting gallium on a crystalline aluminosilicate by a known method such as an ion exchange method or an impregnation method. The gallium source used in this case is not particularly limited, and examples thereof include gallium salts such as gallium nitrate and gallium chloride, and gallium oxide.
The zinc-supporting crystalline aluminosilicate is obtained by supporting zinc on a crystalline aluminosilicate by a known method such as an ion exchange method or an impregnation method. Although it does not specifically limit as a zinc source used in that case, Zinc salts, such as zinc nitrate and zinc chloride, zinc oxide, etc. are mentioned.

  When the cracking reforming reaction catalyst contains gallium and / or zinc, the content of gallium and / or zinc in the cracking reforming reaction catalyst is 0.01-5. The content is preferably 0% by mass, and more preferably 0.05 to 2.0% by mass. If the content of gallium and zinc is 0.01% by mass or more, the production rate of monocyclic aromatic hydrocarbons can be increased, and if it is 5.0% by mass or less, the yield of monocyclic aromatic hydrocarbons Can be higher.

The catalyst for cracking and reforming reaction is made into, for example, a powder form, a granular form, a pellet form or the like according to the reaction format. For example, in the case of a fluidized bed, it is in the form of powder, and in the case of a fixed bed, it is in the form of particles or pellets. The average particle size of the catalyst used in the fluidized bed is preferably 30 to 180 μm, more preferably 50 to 100 μm. The bulk density of the catalyst used in the fluidized bed is preferably 0.4 to 1.8 g / cc, more preferably 0.5 to 1.0 g / cc. In addition, an average particle diameter represents the particle size used as 50 mass% in the particle size distribution obtained by the classification by a sieve, and a bulk density is the value measured by the method of JIS specification R9301-2-3. When obtaining a granular or pellet-shaped catalyst, if necessary, an inert oxide may be blended into the catalyst as a binder and then molded using various molding machines.
When the cracking reforming reaction catalyst contains an inorganic oxide such as a binder, a binder containing phosphorus may be used.

  The reaction temperature when the raw material oil is brought into contact with and reacted with the catalyst for cracking reforming reaction is not particularly limited, but is preferably 400 to 650 ° C. If the minimum of reaction temperature is 400 degreeC or more, raw material oil can be made to react easily, More preferably, it is 450 degreeC or more. Moreover, if the upper limit of reaction temperature is 650 degrees C or less, the yield of monocyclic aromatic hydrocarbon can be made high enough, More preferably, it is 600 degrees C or less.

  The reaction pressure when the feedstock oil is brought into contact with and reacted with the cracking reforming reaction catalyst is preferably 1.5 MPaG or less, and more preferably 1.0 MPaG or less. If the reaction pressure is 1.5 MPaG or less, the by-product of light gas can be suppressed and the pressure resistance of the reactor can be lowered.

  The contact time between the feedstock and the cracking reforming reaction catalyst is not particularly limited as long as the desired reaction proceeds substantially. For example, the gas passage time on the cracking reforming reaction catalyst is 1 to 300 seconds. Further, the lower limit is more preferably 5 seconds or more, and the upper limit is more preferably 150 seconds or less. If the contact time is 1 second or longer, the reaction can be performed reliably, and if the contact time is 300 seconds or shorter, accumulation of carbonaceous matter in the catalyst due to coking or the like can be suppressed. Or the generation amount of the light gas by decomposition | disassembly can be suppressed.

By separating the cracking and reforming reaction product generated from the cracking and reforming reaction into fractions having predetermined properties, the cracking and reforming gasoline base material according to the present invention can be produced.
In order to separate the cracking and reforming reaction product into predetermined fractions, a known distillation apparatus or gas-liquid separation apparatus can be used. As an example of a distillation apparatus, what can distill and isolate | separate a some fraction with a multistage distillation apparatus like a stripper is mentioned. As an example of the gas-liquid separation device, a gas-liquid separation tank, a product introduction pipe for introducing a product into the gas-liquid separation tank, a gas component outflow pipe provided at an upper part of the gas-liquid separation tank, What comprises the liquid component outflow pipe | tube provided in the lower part of the gas-liquid separation tank is mentioned.
The cracked and reformed gasoline base material according to the present invention is preferably a fraction mainly containing hydrocarbons having 7 and 8 carbon atoms.

  The cracked and reformed gasoline base material according to the present invention is obtained by the above-described production method and has the following properties.

  The total aromatic content of the cracked and reformed gasoline base material according to the present invention is 90% by volume or more, preferably 98% by volume or more, and more preferably 99% by volume or more. The total aromatic content here means the content of the aromatic content measured according to JIS K2536 “Petroleum products—component test method”.

The aromatic component having 8 carbon atoms of the cracked and reformed gasoline base material according to the present invention is 5% by volume or more and 50% by volume or less.
The aromatic component having 9 or more carbon atoms of the cracked and reformed gasoline base material according to the present invention is 30% by volume or less, preferably 25% by volume or less, more preferably 20% by volume or less. Here, the aromatic content having 8 or 9 or more carbon atoms means the content of the aromatic content measured by JIS K2536 “Petroleum product-component test method”.

  The olefin content of the cracked and reformed gasoline base material according to the present invention is 5% by volume or less, preferably 3% by volume or less, and more preferably 1% by volume or less. The olefin content mentioned here is a value measured according to JIS K2536 “Petroleum products-component test method”.

  The sulfur content of the cracked and reformed gasoline base material according to the present invention is 20 mass ppm or less, preferably 10 mass ppm or less, more preferably 5 mass ppm or less. The sulfur content mentioned here is a value measured according to JIS K2541 “Crude oil and petroleum products—Sulfur content test method”.

  The research octane number of the cracked and reformed gasoline base material according to the present invention is 110 or more. The research octane number referred to here is a value measured by JIS K2280 “Petroleum products—fuel oil—octane number and cetane number test method and cetane index calculation method”.

The density at 15 ° C. of the cracked and reformed gasoline base material according to the present invention is 0.8 g / cm ³ or more and 0.95 g / cm ³ or less. Here, the density at 15 ° C. is a value measured according to JIS K2249 “Crude oil and petroleum products—density test method and density / mass / capacity conversion table”.

In the method for producing a gasoline composition of the present invention, in addition to the cracked and reformed gasoline base material, the catalytic cracked gasoline base material is 10 to 90% by volume and the hydrocarbon base material having 4 carbon atoms based on the total amount of the gasoline composition. 0.1-10 volume% is mix | blended.
As catalytic cracking gasoline base material, catalytic cracking gasoline (full range cracking gasoline) obtained by catalytic cracking method, light fraction of catalytic cracking gasoline (light cracking gasoline), medium fraction of catalytic cracking gasoline (medium cracking gasoline) , A heavy fraction of catalytic cracking gasoline (heavy cracking gasoline), and a hydrocarbon base material having 4 carbon atoms is butane obtained from crude oil distillation equipment, naphtha reforming equipment, alkylation equipment, etc. Examples include straight-cut butane fractions centered on them, straight-run desulfurized butane cuts centered on butane obtained by desulfurizing them, and cracked butane fractions centered on butane / butene obtained from catalytic cracking equipment, etc. Specifically, it is a base material containing normal butane, isobutane, 1 butene, 2 butene, iso-2-butene, butadiene and butyne.

  In the method for producing a gasoline composition according to the present invention, as long as a predetermined amount of a predetermined cracked reformed gasoline base, a catalytic cracked gasoline base, and a hydrocarbon base having 4 carbon atoms is blended in a predetermined amount, other gasoline bases are blended. Are not particularly limited, but specifically, for example, straight-run propane fractions mainly composed of propane obtained from crude oil distillation equipment, naphtha reforming equipment, alkylation equipment, etc., straight-run desulfurization propane fractions obtained by desulfurizing them. , Propane / propylene cracked propane fraction obtained from catalytic crackers, naphtha fraction (full range naphtha) obtained by atmospheric distillation of crude oil, naphtha light fraction (light naphtha), naphtha Heavy fraction (heavy naphtha), desulfurized full-range naphtha desulfurized full-range naphtha, desulfurized light naphtha desulfurized light naphtha, desulfurized heavy naphtha desulfurized heavy naphtha Alkaline obtained by adding (alkylating) lower olefins to hydrocarbons such as isomerized gasoline and isobutane obtained by converting naphtha and light naphtha to isoparaffin using an isomerizer, modified by catalytic reforming method Quality raffinate, a residue of aromatics extracted from reformed gasoline, light fraction of reformed gasoline (light reformed gasoline), medium heavy fraction of reformed gasoline (medium heavy reformed gasoline) FT (Fischer-Tropsch) after cracking heavy fraction of reformed gasoline (heavy reformed gasoline), hydrocracked gasoline obtained by hydrocracking process, natural gas, etc. into carbon monoxide and hydrogen ) One or more kinds of base materials such as a light fraction of GTL (Gast Liquids) obtained by synthesis can be mixed. Among these gasoline base materials, base materials such as heavy naphtha, light reformed gasoline, medium quality reformed gasoline and alkylate are preferably used.

  In the method for producing a gasoline composition according to the present invention, an oxygen-containing compound may be further blended as necessary in addition to the oxygen-containing compound that can be inherently contained in a gasoline base material. Examples of the oxygen-containing compound to be blended include alcohols having 2 to 4 carbon atoms and ethers having 4 to 8 carbon atoms. Specific examples of the oxygen-containing compound include ethanol, methyl-tert-butyl ether (MTBE), ethyl-tert-butyl ether (ETBE), tert-amyl methyl ether (TAME), and tert-amyl ethyl ether. Methanol is not preferable because the aldehyde concentration in the exhaust gas may be high and corrosive.

  The content of the oxygen-containing compound in the gasoline composition of the present invention is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, most preferably in terms of oxygen element, based on the total amount of the composition. Preferably it is 2.0 mass% or less. When it exceeds 5.0 mass%, NOx in exhaust gas may increase. The content of oxygen-containing compounds referred to here is the sum of the contents of oxygen-containing compounds that can be inherently contained in gasoline base materials and the like, and the contents of the oxygen-containing compounds added as additives. means.

  Moreover, in the manufacturing method of the gasoline composition which concerns on this invention, in order to improve the oxidation stability, it is preferable to mix | blend an antioxidant further. Specific examples of the antioxidant include N, N′-diisopropyl-p-phenylenediamine, N, N′-diisobutyl-p-phenylenediamine, 2,6-di-t-butyl-4-methylphenol, Known compounds such as hindered phenols can be used as gasoline antioxidants.

  Furthermore, in the method for producing a gasoline composition according to the present invention, it is preferable to add a metal deactivator. Examples of the metal deactivator include amine carbonyl condensation compounds such as N, N′-disalicylidene-1,2-diaminopropane. The compounding amount of the metal deactivator is preferably 0 to 100 g / kL, more preferably 0 to 10 g / kL based on the total amount of the gasoline composition.

  Further, in the method for producing a gasoline composition according to the present invention, a surface ignition preventing agent such as an organic phosphorus compound; an anti-icing agent such as a polyhydric alcohol or an ether thereof; an alkali metal salt or an alkaline earth metal salt of an organic acid; Ancillary surfactants; cationic surfactants; antistatic agents such as amphoteric surfactants; colorants such as azo dyes; organic carboxylic acids or their derivatives; alkenyl succinic acid Rust preventive agents such as esters; draining agents such as sorbitan esters; discriminating agents such as kilyzanine and coumarin; and odorants such as natural essential oil synthetic fragrances may be blended as necessary. These additives can be added singly or in combination of two or more. The total content of these additives is preferably 0.1% by mass or less based on the total amount of the composition.

The research octane number (RON) of the gasoline composition of the present invention needs to be 89 or more and less than 96.
The research method octane number (RON) of the gasoline composition of the present invention is required to be 89 or more and preferably 90 or more from the viewpoint of preventing knocking and improving acceleration and drivability. In addition, the RON of the gasoline composition of the present invention is a reduction in the amount of carbon dioxide emission during driving when used mainly in a regular gasoline specification vehicle from the increase in carbon dioxide emission during the production of the gasoline composition. In order to increase the size, it is necessary to be less than 96.
Further, the motor method octane number (MON) of the gasoline composition of the present invention is preferably 80 or more from the viewpoint of improving the anti-knocking performance during high speed running.
The research method octane number and the motor method octane number referred to in the present invention mean the research method octane number and the motor method octane number measured by JIS K2280 “Octane number and cetane number test method”, respectively.

In the gasoline composition of the present invention, from the viewpoint of ensuring the output performance of the engine, the density at 15 ° C. of the fraction having a boiling point range of 100 to 150 ° C. is preferably 0.730 g / cm ³ or more, It is preferably 0.860 g / cm ³ or less.
The density at 15 ℃ gasoline compositions of the present invention (the density of the overall composition) is preferably 0.783g / cm ³ or less, 0.765 g / cm ³ or less is more preferable. The lower limit is preferably 0.710 g / cm ³ or more. If the density of the gasoline is less than 0.710 g / cm ³ , the fuel efficiency may be deteriorated. On the other hand, if it exceeds 0.783 g / cm ³ , the acceleration performance may be deteriorated and the plug may be smoldered. .
In addition, the density as used in the field of this invention means the density measured by JISK2249 "The density test method and density / mass / capacity conversion table of crude oil and petroleum products".

  The sulfur content of the gasoline composition of the present invention is preferably 10 ppm by mass or less, and more preferably 8 ppm by mass or less. If the sulfur content exceeds 10 ppm by mass, the performance of the exhaust gas treatment catalyst may be adversely affected, and the concentration of NOx, CO, and HC in the exhaust gas may increase, and the amount of benzene emitted is also high. May increase. In addition, content of the sulfur content as used in the field of this invention means the sulfur content measured by JISK2541 "Crude oil and petroleum products-sulfur content test method".

The total aromatic content of the gasoline composition of the present invention is preferably 35% by volume or less.
The aromatic component contained in the gasoline composition of the present invention includes, for example, benzene having 6 carbon atoms, toluene having 7 carbon atoms, xylene and ethylbenzene having 8 carbon atoms, and 1,2 having 9 carbon atoms. , 4-trimethylbenzene, 1-methyl-3-ethylbenzene and the like, and C1-C1,3-diethylbenzene and the like are included.

In the gasoline composition of the present invention, it is preferable that the aromatic content derived from the cracked and reformed gasoline base relative to the total aromatic content in the gasoline composition satisfies the following formula (1). The “aromatic content derived from cracked and reformed gasoline base material” and the “content of total aromatic content in gasoline composition” as used in the present invention are based on JIS K2536 “Petroleum product-component test method”. Means the aromatic content (unit: volume%) derived from the cracked and reformed gasoline base material and the total aromatic content (unit: volume%) in the gasoline composition.
0.1 ≦ A / B ≦ 1.0 (1)
(In the formula, A represents the content (volume%) of the aromatic component derived from the cracked and reformed gasoline base material, and B represents the content (volume%) of the total aromatic content in the gasoline composition.)

  In addition, from the viewpoint of reduction of combustion chamber deposits and reduction of exhaust gas, the content of aromatics derived from cracked and reformed gasoline base relative to the content of total aromatics in the gasoline composition represented by the above formula (1) The ratio (A / B) of the amount is more preferably 0.2 or more, and further preferably 0.3 or more.

  In the gasoline composition of the present invention, if the content of the aromatic component derived from the cracked and reformed gasoline base relative to the total aromatic content in the gasoline composition satisfies the above formula (1), the aromatic content The breakdown is not particularly limited, but the ratio of the aromatic hydrocarbon having 9 or more carbon atoms in the gasoline composition is preferably 20% by volume or less, more preferably 18% by volume or less, and more preferably 15% by volume or less. More preferably, it is not more than volume%.

  The benzene content in the gasoline composition of the present invention is preferably 1% by volume or less, and more preferably 0.5% by volume or less. The benzene content referred to in the present invention means a value measured according to JIS K2536 “Petroleum product-component test method”.

  The olefin content of the gasoline composition of the present invention is preferably 30% by volume or less, and more preferably 25% by volume or less. When the olefin content exceeds 30% by volume, there is a possibility that the oxidation stability of gasoline is deteriorated and intake valve deposit is increased, and engine exhaust gas is deteriorated. The olefin content referred to in the present invention means the content (volume%) of the olefin content in the gasoline composition measured according to JIS K2536 “Petroleum products—component test method”.

  Regarding the distillation properties of the gasoline composition of the present invention, the 10 vol% distillation temperature (T10) is preferably 70 ° C. or lower, and more preferably 65 ° C. or lower. When T10 exceeds 70 ° C., there is a possibility that a problem occurs in the low-temperature startability. On the other hand, T10 is preferably 35 ° C. or higher. If T10 is less than 35 ° C., hydrocarbons in the exhaust gas may increase, and vapor lock may cause a problem in high-temperature operability.

  The 50 volume% distillation temperature (T50) of the gasoline composition of the present invention is preferably 110 ° C. or lower from the viewpoint of improving acceleration and suppressing increase in hydrocarbons (HC) in the exhaust gas. ° C or lower is more preferable, 100 ° C or lower is further preferable, and 90 ° C or lower is most preferable. Further, T50 is preferably 75 ° C. or higher, and more preferably 78 ° C. or higher, from the viewpoint of preventing deterioration of fuel consumption.

  The 90 volume% distillation temperature (T90) of the gasoline composition of the present invention prevents malfunctions in low-temperature operability during cold operation, suppresses increase in hydrocarbons in exhaust gas, and increases dilution of engine oil with gasoline. From the viewpoints of suppression, suppression of increase in intake valve deposit, suppression of increase in combustion chamber deposit, suppression of engine oil deterioration, and generation of sludge, the temperature is preferably 180 ° C or lower, and 170 ° C or lower. Is more preferable. Further, T90 is preferably 115 ° C. or higher from the viewpoint of preventing deterioration of fuel consumption.

  The distillation end point (EP) of the gasoline composition of the present invention is preferably 215 ° C. or less from the viewpoint of suppressing increase in intake valve deposits and combustion chamber deposits and preventing plug smoldering. Is more preferable.

  The 70 ° C. distillate (E70) of the gasoline composition of the present invention is preferably 40% by volume or less from the viewpoint of improving acceleration and suppressing increase in hydrocarbons (HC) in the exhaust gas. Moreover, it is preferable that E70 is 25 volume% or more from a viewpoint of preventing a fuel consumption deterioration.

  In the present invention, T10, T50, T90, EP and E70 mean T10, T50, T90, EP and E70 measured by JIS K2254 “Petroleum product-distillation test method”, respectively.

  In the gasoline composition of the present invention, the content of dienes is preferably 0.1% by volume or less based on the total amount of the composition from the viewpoint of ensuring the storage stability of the gasoline composition. It is more preferably at most 05% by volume, still more preferably at most 0.01% by volume.

  In the gasoline composition of the present invention, the manganese content is preferably 2 mass ppm or less, the iron content is preferably 2 mass ppm or less, and the sodium content is 2 mass ppm or less. The potassium content is preferably 2 mass ppm or less, and the phosphorus content is preferably 2 mass ppm or less. If these metal components exceed the upper limit, the efficiency of the exhaust gas purification system may be reduced due to an increase in the amount accumulated on the exhaust gas purification catalyst, deterioration of the catalyst carrier, deterioration of the air-fuel ratio sensor, or the like. In the present invention, the contents of manganese, iron and sodium are “combustion ashing-inductively coupled plasma emission method”, the potassium content is “combustion ashing-atomic absorption method”, and the phosphorus content is ASTM D3231 “Standard”. It means the value measured by “Test Method for Phosphorus in Gasoline”.

The measurement of "combustion ashing-inductively coupled plasma emission method" and "combustion ashing-atomic absorption method" can be performed according to the procedures shown in the following (i) to (vi).
(I) A 20 g sample is taken on a platinum dish.
(Ii) 0.4 g of powdered sulfur is added to suppress the volatilization of the component elements, and the volatile matter is removed at 150 ° C. for 1 hour on a sand bath.
(Iii) Burn the residue.
(Iv) Ashing in an electric furnace at 500 ° C. for 2 to 3 hours.
(V) Dissolve in 2-3 mL of concentrated sulfuric acid and make up to 20 mL.
(Vi) Manganese, iron, and sodium contents are analyzed using an inductively coupled plasma emission spectrometer (ICPS-8000, manufactured by Shimadzu Corporation), and phosphorus contents are analyzed using an atomic absorption photometer (Z6100, manufactured by Hitachi, Ltd.). .

  The lead vapor pressure (RVP) of the gasoline composition of the present invention needs to be adjusted depending on the season and region in which the gasoline is used. However, in general, from the viewpoint of preventing malfunctions due to low temperature startability and vapor lock, (May to September) is preferably adjusted to 44 to 65 kPa, more preferably 50 to 65 kPa, and most preferably 55 to 65 kPa. On the other hand, in the winter season (October to April), it is preferably adjusted to 65 to 93 kPa, more preferably 70 to 93 kPa, and most preferably 70 to 90 kPa. The reed vapor pressure in the present invention means a reed vapor pressure (RVP) measured by JIS K2258 “Crude oil and fuel oil vapor pressure test method (reed method)”.

  The oxidation stability of the gasoline composition of the present invention is preferably 240 minutes or more, more preferably 480 minutes or more, and most preferably 600 minutes or more. If the oxidative stability is less than 240 minutes, gums can form during storage. In addition, the oxidation stability as used in the field of this invention means the value measured by JISK2287 "gasoline oxidation stability test method (induction period method)".

  The copper plate corrosion (50 ° C., 3 h) of the gasoline composition of the invention is preferably 1 or less, more preferably 1a. If the copper plate corrosion exceeds 1, the fuel system conduit may corrode. In addition, the copper plate corrosion as used in the field of this invention means the value measured based on JISK2513 "Petroleum product-copper plate corrosion test method" (test temperature 50 degreeC, test time 3 hours).

  The amount of unwashed actual gum in the gasoline composition of the present invention is preferably 20 mg / 100 mL or less, and more preferably 18 mg / 100 mL or less. Moreover, it is preferable that it is 5 mg / 100 mL or less, it is more preferable that it is 2 mg / 100 mL or less, and it is still more preferable that it is less than 1 mg / 100 mL. When the unwashed actual gum amount and the washed actual gum amount exceed the above upper limit, precipitates may be generated in the fuel introduction system, or the suction valve may become stuck. The unwashed actual gum amount and the washed actual gum amount in the present invention mean values measured according to JIS K2261 “Petroleum products—automobile gasoline and aviation fuel oil—existing gum test method—injection evaporation method”.

  The amount of kerosene mixed in the gasoline composition of the present invention is preferably 4% by volume or less, and more preferably 1% by volume or less. The amount of kerosene mixed in the present invention means a value measured by JIS K 2536 “Petroleum product-component test method”.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.

(Gasoline base material)
As base materials for preparing gasoline compositions, butane, light cracked gasoline, medium cracked gasoline, heavy cracked gasoline, full range cracked gasoline, light straight run gasoline, heavy straight run gasoline, medium reformed gasoline, heavy Quality reformed gasoline and cracked reformed gasoline base material were prepared. The properties of each substrate are shown in Tables 1 and 2.

In addition, the cracking reformed gasoline base material shown in Table 2 is a base material obtained by the following method.
Fluid catalytic cracking light oil LCO (10 vol% distillation temperature is 215 ° C, 90 vol% distillation temperature is 318 ° C, density at 15 ° C is 0.9258 g / cm ³ , saturation is 23 vol%, olefin content is 2 vol %, Total aromatic content is 75 vol%), reaction temperature: 538 ° C., reaction pressure: 0.3 MPaG, contact time between LCO and catalyst is 60 seconds in a fluidized bed reactor. The catalyst was brought into contact with and reacted with a catalyst for use (MFI type zeolite carrying 0.2% by mass of gallium and 0.7% by mass of phosphorus and containing a binder) to carry out a decomposition and reforming reaction. Subsequently, the cracking and reforming reaction product was fractionated to produce cracking and reforming gasoline base materials having the properties shown in Table 2.

[Examples 1-5, Comparative Examples 1-3]
In Examples 1 to 5 and Comparative Examples 1 and 3, gasoline compositions having the properties shown in Table 3 were prepared using the base materials shown in Tables 1 and 2, respectively. In addition, as the gasoline composition of Comparative Example 2, commercially available regular gasoline was prepared.
In addition, the property measurement of the gasoline base material and the gasoline composition was performed based on the above-described test method and measurement method.

[Measurement of fuel consumption and emission carbon dioxide]
About each gasoline composition of Examples 1-5 and Comparative Examples 1-2, the fuel consumption measurement by the 10 * 15 mode driving | running | working and the measurement of the exhaust carbon dioxide were implemented using the following test vehicle. The obtained results are shown in Table 3. In addition, in order to grasp the influence of fuel properties properly, the exhaust gas measurement value is a result of engine out.

(Test vehicle)
Engine: Inline 4-cylinder Displacement: 1795cc
Injection system: Multi-point system Drive system: FF

[Combustion chamber deposit test]
About each gasoline composition of Examples 1-5 and Comparative Examples 1-2, the following test engine was used and the combustion chamber deposit test by the JASO method was implemented. The deposit amount after the test is shown in Table 3.
(Test engine)
Engine: Inline 4-cylinder Displacement: 2156cc
Injection method: Multipoint type.

As shown in Table 3, the gasoline compositions of Examples 1 to 5 satisfy the standards of automobile gasoline specified in JIS K2202, and reduce the combustion chamber deposit while maintaining the distillation properties and discharge. It can be seen that it is possible to reduce exhaust gases such as gases (NOx, THC, CO) and CO _2. On the other hand, cracked reformed gasoline base, catalytic cracked gasoline base, and carbon base 4 hydrocarbon base In Comparative Examples 1 and 3 and a commercially available regular gasoline whose blending ratio is outside the scope of claims of the present application, the combustion chamber deposit and exhaust gas are worse than the gasoline composition of the examples, or the standard of automobile gasoline specified in JIS K2202 It may be out of place.

  According to the method of the present invention, it is possible to produce a gasoline composition that can reduce the combustion chamber deposit and the carbon dioxide discharged while maintaining the octane number and the distillation properties, which is extremely useful industrially.

Claims (3)

A feed oil having a 10 vol% distillation temperature of 140 ° C. or more and a 90 vol% distillation temperature of 380 ° C. or less is brought into contact with a catalyst for cracking reforming reaction containing medium pore zeolite and / or large pore zeolite. A hydrocarbon produced by performing a cracking and reforming reaction at a temperature of 400 to 650 ° C., a reaction pressure of 1.5 MPaG or less, and a contact time of 1 to 300 seconds, and has the following properties (1) to (7) A research method characterized by blending at least 1 to 35% by volume of a cracked and reformed gasoline base, 10 to 90% by volume of a catalytically cracked gasoline base, and 0.1 to 10% by volume of a hydrocarbon base having 4 carbon atoms. A method for producing a gasoline composition having an octane number of 89 or more and less than 96.
(1) 90% by volume or more of aromatic content (2) 5% by volume or less of olefin content (3) 5 to 50% by volume of aromatics having 8 carbon atoms
(4) Aromatic content of 9 or more carbon atoms is 30% by volume or less (5) Sulfur content is 20 mass ppm or less (6) Research octane number is 110 or more (7) Density at 15 ° C. is 0.8 to 0.95 g / cm ³ The method for producing gasoline according to claim 1, wherein the cracked and reformed gasoline base material is blended so as to satisfy 0.10 ≦ A / B ≦ 1.0.
(A represents the content (volume%) of the aromatic component derived from the cracked and reformed gasoline base material, and B represents the content (volume%) of the total aromatic content in the gasoline composition.) The said gasoline composition satisfy | fills the following (1)-(7), The manufacturing method of the gasoline composition of Claim 1 or Claim 2 characterized by the above-mentioned.
(1) Density at 15 ° C. is 0.783 g / cm ³ or less (2) Sulfur content is 10 mass ppm or less (3) Total aromatic content is 35% by volume or less (4) Benzene is 1% by volume or less (5) Olefin 30% by volume or less (6) 10% by volume distillation temperature of 70 ° C. or less, 50% by volume distillation temperature of 110 ° C. or less and 90% by volume distillation temperature of 180 ° C. or less (7) Distillation temperature of 70 ° C. Distillation amount (E70) at 40% by volume or less