WO2007114027A1

WO2007114027A1 - Unleaded gasoline composition

Info

Publication number: WO2007114027A1
Application number: PCT/JP2007/055306
Authority: WO
Inventors: Takashi Kaneko
Original assignee: Nippon Oil Corporation
Priority date: 2006-03-31
Filing date: 2007-03-09
Publication date: 2007-10-11

Abstract

An unleaded gasoline composition in which an FT synthesized base material of low octane number can be used as a gasoline base material. There is provided an unleaded gasoline composition characterized by containing the whole or part of fraction of 25° to 220°C distillation temperature range from FT synthesized base material and exhibiting a research octane number of 89.0 or above, a motor octane number of 80.0 or above, a 50% distillation temperature of 75° to 110°C and a sulfur content of 10 ppm by mass or less.

Description

Unleaded gasoline composition

[Technical field]

The present invention relates to an unleaded gasoline composition as a fuel for automobiles, and particularly to an unleaded gasoline composition containing an FT synthetic base material from the viewpoint of diversification of supply sources and excellent in exhaust gas purification performance, fuel consumption performance, and driving performance. Related.

[Background Technology] Rice field

Conventionally, gasoline is manufactured by blending one or more of the base materials of gasoline fraction obtained by processing crude oil with various refining equipment such as catalytic reforming equipment and catalytic cracking equipment. . .

In recent years, gasoline automobiles have been required to reduce both harmful substances in exhaust gas for improving the air environment and to reduce CO ₂ emissions of greenhouse gases from the viewpoint of controlling global warming. In addition to improving vehicle and engine technology including exhaust aftertreatment devices, it is also important to optimize gasoline quality. Gasoline needs quality that draws out the excellent exhaust gas purification performance, fuel efficiency, and driving performance of the vehicle itself. ·

Demand for crude oil, which is a raw material for gasoline, has been increasing against the background of an increase in the number of automobiles owned.Considering that crude oil is a finite resource, diversification of gasoline supply sources, that is, There is a need to produce gasoline from resources other than crude oil and to improve the yield of gasoline that can be produced from crude oil.

In addition, the quality of gasoline obtained by diversifying these supply sources must be excellent in exhaust gas purification performance, fuel efficiency, and drivability.

FT synthetic base material can be used as a raw material for a wide range of carbon-containing materials, so it is effective for diversifying the fuel supply source. However, because of its ignition characteristics, the fuel for automobiles is mainly used for diesel engines. It is considered suitable, and the low octane number is a problem for burning FT synthetic substrates in gasoline engines.

It is also possible to use resources other than crude oil as a compound that can be blended with gasoline. There are alcohols such as ethanol, and ethers such as methyl tertiary butyl ether and ethyl tertiary butyl ether. These alcohols and ethers have high octane numbers, and patent applications focusing on the effect of improving the octane number during mixing have been filed (for example, see Patent Documents 1 to 4).

(1) Patent Document 1 Japanese Unexamined Patent Publication No. 2005-029760

(2) Patent Document 2 Japanese Laid-Open Patent Publication No. 2005-029761

(3) Patent Document 3 Japanese Unexamined Patent Publication No. 2005-029762

(4) Patent Document 4 Japanese Patent Application Laid-Open No. 200.5-029763

[Disclosure of the Invention]

The purpose of the present invention is to diversify the supply sources of gasoline, that is, to produce gasoline from resources other than crude oil, and to improve the yield of gasoline that can be produced from crude oil. The purpose is to provide an unleaded gasoline composition that can efficiently secure the octane number required for gasoline when the source is diversified.

As a result of diligent research to solve the above problems, the present inventors have mixed FT synthetic base materials that can be made from a wide range of carbon-containing substances as raw materials, and have obtained gasoline compositions with specific properties. By stipulating, it becomes possible to diversify gasoline supply sources, and at the same time, it is found that the exhaust gas purification performance, fuel efficiency performance, and driving performance of gasoline automobiles can be extracted. It came. That is, the present invention contains all or a part of the FT synthesis base material having a distillation temperature range of 25 ° C. to 220 ° C., a research octane number of 89.0 or more, a motor method. The present invention relates to an unleaded gasoline composition characterized by an octane number of 80.0 or more, a 50% distillation temperature of 75 ° C or more and 1 10 ° C or less, and a sulfur content of 10 mass ppm or less.

In addition, the present invention contains all or a part of the distillate whose FT synthesis base material has a distillation temperature range of 25 ° C to 220 ° C, has a research octane number of 96.0 or more, a motor octane number of one method 84.0 or more, Sulfur content is 1.0 mass ppm or less, 10% distillation temperature is 70 ° C or less, 50% distillation temperature is 75 ° C or more 1 10 ° C or less, 90% distillation temperature is 1 80 ° C or less, distillation end point 220 ° C or less, lead vapor pressure 44 k Pa or more 9 3'k Pa or less, Density (15 ° C) is 0.6 90 gno cm ³ or more 0.783 g / cm ³ or less, oxidation stability is 240 minutes or more, copper plate corrosion (5.0 ° C, 3 hours ) Is 1 or less, washed real gum is 5 mgZ 100 ml or less, unwashed real gum is 30 mg / l 00 ml or less, and the benzene content is 1% by volume or less.

Further, the present invention contains all or a part of a fraction having a distillation temperature range of 25 ° C. to 220 ° C. of the FT synthesis base material, and has a research method octane number of 89.0 or more and less than 96.0, Motor method octane number is 80..0 or more, sulfur content is 10 'mass ppm or less, 10% distillation temperature is 70 ° C or less, 50% distillation temperature is 75 ° C or more 1 1 0 ° C Less than,

90% distillation temperature is 1 80 ° C or less, distillation end point is 220 ° C or less, reed vapor pressure is 44 k Pa or more and 9 3 k Pa or less, density (15 ° C) is 0.6 90 g cm ³ or more 0.7 83 g / cm ³ or less, oxidation stability is 240 minutes or more, copper plate corrosion (50 ° C, 3 hours) is 1 or less, cleaning actual gum is 5 mg / 100 ml or less, unwashed actual 30 mg of gum /

100 ml or less, and the benzene content is 1% by volume or less.

In addition, the present invention provides a FT synthesis base material having a distillation temperature range of 25 ° C. to 220 ° C. or a partial content (volume%) of A and a C 4-8 ether. When the content (volume%) of the alcohol is B and the content (volume%) of the alcohol having 2 to 4 carbon atoms is C, the following equations (1) to (5) are satisfied, and research The octane number of the method is 89.0 or more, the octane number of the motor method is 80.0, the 50% distillation temperature is 75 ° C or more and 110 ° C or less, and the sulfur content is 10 mass p pm or less. It is related with the above-mentioned unleaded gasoline composition characterized by these.

(1) 50≥ A> 0

(2) B + C> 0

(3) 25≥B≥ 0

(4) 1 5≥C≥ 0

(5) A / (B + C) ≥ 1

[Best Mode for Carrying Out the Invention]

Hereinafter, the present invention will be described in detail. The gasoline of the present invention needs to contain an FT synthetic base material. Here, the FT synthetic base material is a naphtha obtained by applying a Fischer-Tropsch (FT) reaction to a mixed gas containing hydrogen and carbon monoxide as main components (sometimes referred to as synthetic gas). , Kerosene, a liquid fraction equivalent to diesel oil, and a hydrocarbon mixture obtained by hydrotreating and hydrocracking these, and a liquid fraction and FT wax by the FT reaction, This refers to a base material composed of a hydrocarbon mixture obtained by hydrorefining and hydrocracking.

The mixed gas used as the raw material for the FT synthesis base material is a carbon-containing substance that is oxidized using oxygen and / or water and / or carbon dioxide as an oxidant, and, if necessary, a shift reaction using water. By adjusting to the predetermined hydrogen and carbon monoxide concentrations.

Carbon-containing substances include natural gas, petroleum liquefied gas, methane gas, etc., gas components composed of hydrocarbons that are gaseous at room temperature, petroleum asphalt, biomass, coal, waste materials such as building materials and garbage, sludge, In general, mixed gas obtained by exposing heavy crude oil, unconventional petroleum resources, etc., which are difficult to process by ordinary methods to high temperatures, is mainly composed of hydrogen and carbon monoxide. As long as a mixed gas is obtained, the present invention does not limit the raw materials.

The Fischer-Tropsch reaction requires a metal catalyst. Preferably, the method uses a group 8 metal of the periodic table, for example, cobalt, ruthenium, rhodium, palladium, nickel, iron, etc., more preferably a group 8 group 4 metallurgy as an active catalyst component. It is also possible to use a metal group in which appropriate amounts of these metals are mixed. These active metals are generally used in the form of a catalyst obtained by being supported on a support such as silica, alumina, titania or silica alumina. Further, the catalyst performance can be improved by using these catalysts in combination with the second metal in addition to the active metal. Examples of secondary metals include zirconium, hafnium, titanium dioxide, etc., in addition to alkaline metals such as sodium, lithium, and magnesium, and alkaline metals, such as improved conversion of carbon monoxide and wax. It is used as appropriate depending on the purpose, such as an increase in chain growth probability, which is an indicator of the amount produced.

The Fischer-Tropsch reaction is a synthesis method that uses a mixed gas as a raw material to produce a liquid fraction and FT wax. In order to perform this synthesis method efficiently, It is preferable to control the ratio of hydrogen to carbon monoxide in the mixed gas. The molar mixing ratio of hydrogen to carbon monoxide (hydrogen monoxide) is preferably 1. The ratio is more preferably 5 or more, and still more preferably 1.8 or more, and the ratio is preferably 3 or less, more preferably 2.6 or less> 2 Even more preferably, it is 2 or less.

When performing the Fischer-Tropsch reaction using the above catalyst, the reaction temperature is preferably 180 ° C. or higher and 320 ° C. or lower, and preferably 20 ° C. or higher and 30 ° C. or lower. More preferred. When the reaction temperature is less than 1.80 ° C, carbon monoxide hardly reacts and the hydrocarbon yield tends to be low. In addition, when the reaction temperature exceeds 3220 ° C, the amount of methane and other gases produced increases, and the production efficiency of liquid fractions and FT tuss declines.

The gas space velocity with respect to the catalyst is not particularly limited, but is preferably 5 0 0 h— ¹ or more and 4 0 0 0 h, ¹ or less, more preferably 1 0 0 0 h— ¹ or more and 3 0 0 0 h— ¹ or less. If the gas space velocity is less than 5 00 h— ¹ , the productivity of liquid fuel tends to decrease, and if it exceeds 4 0 0 h— ¹ , the reaction temperature must be increased and gas generation is not possible. It becomes large and the yield of the target product decreases. .

The reaction pressure (partial pressure of synthesis gas composed of carbon monoxide and hydrogen) is not particularly limited, but is preferably 0.5 MPa or more and 7 MPa or less, and more preferably 2 MPa or more and 4 MPa or less. If the reaction pressure is less than 0.5 M Pa, the yield of liquid fuel tends to decrease, and if it exceeds 7 M Pa, the capital investment tends to be six, which tends to be uneconomical.

The FT synthesis substrate is prepared by hydrorefining or hydrocracking the liquid fraction and FT wax produced by the above FT reaction by any method as necessary to obtain the distillation properties, composition, etc. suitable for the purpose. It is also possible to adjust. Hydrorefining and hydrocracking may be selected according to the purpose, and the selection of either one or a combination of both methods is not limited in any way as long as the fuel composition of the present invention can be produced. . The catalyst used for hydrorefining is generally a catalyst in which a hydrogenation active metal is supported on a porous support, but the present invention does not limit the form of the catalyst as long as the same effect can be obtained. ,.

An inorganic oxide is preferably used as the porous carrier. Specific examples include alumina, titania, zirconia, polya, silica, and zeolite. Zeolite is a crystalline aluminosilicate, and examples thereof include faujasite, pentasil, mordenite, etc., preferably faujasite, beta, and mordenite, particularly preferably Y type and beta type. Among them, the Y type is preferably ultra-stabilized.

As the active metal, the following two types (active metal A type and active metal B type) 'are preferably used.

The active metal A-type is at least one metal selected from Group 8 metals of the Periodic Table. Preferably, it is at least one selected from Ru, Rh, Ir, Pd and Pt, and more preferably Pd and / or Pt. The active metal may be a combination of these metals. For example, P t— P d, P t—Rh, P t— Ru, I r — Pd I r _Rh, I r— Ru, P t— P d-Rh, Pt-Rh-Ru, Ir-Pd-Rh> Ir_Rh-Ru. When using a noble metal catalyst composed of these metals, it can be used after pre-reduction treatment in a hydrogen stream. In general, when a gas containing hydrogen is circulated and heat of 200 ° C. or higher is applied according to a predetermined procedure, the active metal on the catalyst is reduced, and hydrogenation activity is exhibited. .

The active metal B type contains at least one metal selected from Group 6A and Group 8 metals of the periodic table, and preferably two or more types selected from Groups 6A and 8 Those containing a metal can also be used. For example, Co-Mo, Ni-Mo, Ni-Co-Mo, Ni.-W can be mentioned, and it is necessary to include a presulfidation step when using a metal sulfide catalyst composed of these metals. .

As the metal source, a general inorganic salt or a complex salt compound can be used, and as a loading method, any of the loading methods used in ordinary hydrogenation catalysts such as impregnation method and ion exchange method should be used. Can do. When a plurality of metals are supported, they may be supported simultaneously using a mixed solution, or may be sequentially supported using a single solution. The metal solution may be an aqueous solution or an organic solvent.

The reaction temperature when hydrorefining using an active metal type A catalyst is preferably 180 ° C or higher and 400 ° C or lower, more preferably .200 ° C or higher and 370 ° C or lower. The temperature is more preferably 250 ° C. or higher and 350 ° C. or lower, and even more preferably 280 ° C. or higher and 350 ° C. or lower. The reaction temperature in hydrorefining is A temperature exceeding 370 ° C is not preferable because side reactions that decompose into a naphtha fraction increase and the yield of the middle fraction extremely decreases. On the other hand, if the reaction temperature is lower than 270 ° C., the alcohol content cannot be completely removed, which is not preferable.

The reaction temperature when hydrotreating using a catalyst composed of an active metal B type is preferably 170 ° C or higher and 320 ° C or lower, more preferably 1 75 ° C or higher and 300 ° C or lower. 1 80 ° C or more and 280 ° C or less is more preferable. If the reaction temperature in hydrorefining exceeds 320 ° C, the side reaction that decomposes into the naphtha fraction increases and the yield of the middle fraction is extremely reduced. Also, if the reaction temperature is below 170 ° C, the alcohol content cannot be completely removed, which is preferable.

The hydrogen pressure when hydrotreating using a catalyst comprising an active metal A type is preferably 0.5 MPa or more and 1 2 MPa or less, and should be 1. OMP a or more and 5. OMP a or less. More preferred. The higher the hydrogen pressure, the more hydrogenation reaction is promoted, but generally there is an optimal point economically.

The hydrogen pressure when hydrotreating using a catalyst composed of an active metal B type is preferably 2 MPa or more and 10 MPa or less, and more preferably 2.51 ^ & 81? Preferably, it is 3 MPa or more and 7 MPa or less. The higher the hydrogen pressure, the more hydrogenation reaction is promoted, but generally there is an optimal point economically. '

The liquid hourly space velocity (LHSV) when performing hydrorefining using a catalyst composed of an active metal type A is preferably from 0. lh— ^{1 to} 10.0 h and ¹ or less, 0.3 h— ¹ or 3. it is more preferably 5 h- ¹ below. The lower LHSV is, the better the reaction is. However, if it is too low, an extremely large reaction column volume is required, which is an excessively large capital investment, which is not economically preferable.

The liquid hourly space velocity which hydrorefining is carried out using a catalyst composed of the active metal B type (LHSV) is preferably 0. 1 h- ¹ or more 2 h- ¹ or less, 0. 2 h- ¹ or more 1. more preferably 5 h- ¹ or less, and more preferably 0. 3 h- ¹ or more 1 is under 2 h- ¹ or more. The lower the LHSV, the better the reaction. However, if the LHSV is too low, an extremely large reaction tower volume is required, resulting in excessive capital investment, which is not economically preferable. ' The hydrogen Z oil ratio when hydrorefining using an active metal type A catalyst is preferably 501 ^ 1 ^ or more and 1000 NLZL or less, and is 7 ONL / ^ L or more and 80 ONL / L or less. More preferably. The higher the hydrogen oil ratio, the more hydrogenation reaction is promoted, but generally there is an optimal point economically.

The hydrogen Z oil ratio when hydrorefining using an active metal B type catalyst is preferably 10 ONLZL or more and 80 ON L / L or less, and 1 20 NL / L or more and 600 NLZL or less. More preferably, it is more preferably 150 NLZL or more and 500 NLZL or less. A higher hydrogen / oil ratio promotes the hydrogenation reaction, but generally there is an optimal point in the economy.

The catalyst used for hydrocracking is generally a catalyst in which a hydrogenation-active metal is supported on a carrier having a solid acid property. However, the present invention limits the form of the catalyst as long as the same effect can be obtained. It is not a thing. ,.

Carriers having solid acid properties include amorphous and crystalline zeolites. Specific examples include amorphous silica-alumina, silica-magnesia, silica-zircouire, silica-titaure and zeolite-type faujasite, beta, MFI, and mordenite. Preferred are zeolite, beta, MF I and mordenite zeolites, more preferably Y and beta. The Y type is preferably ultra-stabilized.

The following two types of active metals (active metal A type and active metal B type) are preferably used. .

The active metal A type is mainly at least one metal selected from Group 6A and Group 8 metals of the Periodic Table. Preferred is at least one metal selected from Ni, Co, Mo, Pt, Pd and W. When using precious metal catalysts made of these metals, they can be used after pre-reduction treatment in a hydrogen stream. In general, when a gas containing hydrogen is circulated and heat of 200 ° C. or higher is applied according to a predetermined procedure, the active metal on the catalyst is reduced, and hydrogenation activity is exhibited.

The active metal B type may be a combination of these metals, such as Pt—P d, Co—Mo, Ni Mo, Ni—W, Ni—Co—Mo. It is done. Also, when using these metal-based catalysts, use them after presulfiding. It is preferable to do this.

As the metal source, a general inorganic salt or a complex salt compound can be used, and as a loading method, any of the loading methods used in usual hydrogenation catalysts such as impregnation method and ion exchange method should be used. Can do. When a plurality of metals are supported, they may be supported simultaneously using a mixed solution, or may be sequentially supported using a single solution. The metal solution may be an aqueous solution or an organic solvent.

The reaction temperature when hydrocracking using a catalyst composed of active metal A type and active metal B type is preferably 200 ° C or higher and 450 ° C or lower, and 250 ° C or higher and 430 ° C or lower. More preferably, it is 300 ° C or more and 400 ° C or less. When the reaction temperature in hydrocracking exceeds 450 ° C, side reactions that decompose into naphtha fractions increase and the yield of middle fractions is extremely unfavorable. On the other hand, when the temperature is lower than 200 ° C, the activity of the catalyst is remarkably lowered.

The hydrogen pressure when hydrocracking using a catalyst comprising an active metal A type and an active metal B type is preferably not less than IMP a and not more than 2 OMP a, and not less than 4 MP a and not less than 16 MP a More preferably, it is more preferably 6 MP.a or more and 1 3 MPa or less. The higher the hydrogen pressure is, the more the hydrogenolysis reaction is promoted, but the progress of the decomposition reaction is rather slow, and the progress of the reaction needs to be adjusted by increasing the reaction temperature, leading to a decrease in catalyst life. Therefore, there is generally an economic optimal point for the reaction temperature.

The liquid hourly space velocity which hydrocracking is carried out using a catalyst composed of the active metal A type (LHS V) is preferably 0. 1 h- ¹ or more 10 h- ¹ or less, 0. 3 h one ¹ More preferably, it is 3.5 h- ¹ or less. The lower LHS V is, the more advantageous it is for the reaction. However, if it is too low, an extremely large reaction tower volume is required, resulting in excessive capital investment, which is not economical.

The liquid hourly space velocity of which hydrocracking is carried out using a catalyst composed of the active metal B type (LHSV) is preferably 0. 1 h- ¹ or more 2 h- ¹ or less, 0. 2 h one ¹ or 1. more preferably 7 h one ¹ below. it is further preferred 0. 3 h- ¹ or more 1 is S h- ¹ below. The lower LHS V is, the better the reaction is. However, if it is too low, a very large reaction tower volume is required, which leads to excessive capital investment. It is not desirable.

The ratio of hydrogen oil when hydrocracking using an active metal type A catalyst is preferably 501 ^ 1: 1 ^ or more and 100 ONLZL or less, and 7 ONL / L or more and 800 NLZL or less. Is more preferably 40 ONL ^/ L or more and 1 500 NLZL or less. A higher hydrogen / oil ratio promotes the hydrogenation reaction, but generally there is an optimal point in the economy.

The hydrogen / oil ratio when hydrocracking using an active metal B type catalyst is preferably 150 NLZL or more and 2000 NL 丄 or less, and may be '300 NLZ L or more and 1 700 NL / L or less. More preferably, it is 400 NL / L or more and 1 500 NL / L or less. A higher hydrogen / oil ratio promotes the hydrogenation reaction, but generally there is an optimal point in the economy.

The apparatus for hydrotreating may have any configuration, the reaction towers may be used alone or in combination, and hydrogen may be additionally injected between the reaction towers, gas-liquid separation operation, hydrogen sulfide removal equipment, It may have a distillation column to fractionate the hydrogenated product and obtain the desired fraction.

The reaction format of the hydrotreating equipment can be a fixed bed system. Hydrogen can take either a countercurrent or cocurrent flow format with respect to the feedstock, or it can have a plurality of reaction towers and a combination of countercurrent and cocurrent flow. The general format is downflow, and there is a gas-liquid co-current format. Hydrogen gas may be injected into the middle column of the reaction tower as a tent to remove reaction heat or increase the hydrogen partial pressure.

The FT synthesis base material contained in the gasoline of the present invention needs to be all or a part of a fraction having a distillation temperature range of 25 to 220 ° C.

Examples of the fraction range include a light fraction of 25 ° C to 70 ° C, a middle fraction of 70 ° C to 160 ° C, and a heavy fraction of 160 ° C to 220 ° C. In addition, the remainder obtained by removing a part of the fraction range from the fraction of 25 ° C to 2,0 ° C can be used.

The normal paraffin content in the FT synthetic base contained in the gasoline of the present invention is 75 volumes. / ₀ or less is preferable, 60% by volume or less is more preferable, and 50% by volume or less is more preferable. If the amount of normal paraffin exceeds 75% by volume, the octane number may decrease, causing knocking resistance, acceleration, and drivability to decrease. May not be diversified.

The isoparaffin content in the FT synthetic substrate contained in the gasoline of the present invention is preferably 20% by volume or more, more preferably 40% by volume or more, and more preferably 50% by volume or more. More preferably, it is most preferably 60% by volume or more. If the amount of normal paraffin is less than 20% by volume, the Otatan number will decrease, which may cause a decrease in knocking resistance, acceleration and drivability, and the blending amount in gasoline will be limited. May not be diversified.

As the FT synthetic substrate contained in the gasoline of the present invention, those having an olebuin content of 5% by volume or more can be preferably used. By the This Orefin is 5 volume ^_0/0 above, antiknock properties, acceleration, there is a possibility of improving drivability.

The gasoline of the present invention has an FT synthesis group consisting of all or part of a distillate whose temperature range is from 25 ° C to 220 ° C. Therefore, it is preferably 3% by volume or more based on the total amount of gasoline, more preferably 5% by volume or more, and 7% by volume. / ₀ or more is more preferable, and 10% by volume or more is even more preferable.

On the other hand, from the viewpoint of fuel efficiency, the content of the base material is preferably 50% by volume or less, more preferably 40% by volume or less, and 30% by volume or less. Is more preferable. In addition, when the gasoline of the present invention is mainly used in a premium gasoline specification vehicle, the content of the base material is particularly preferably 25% by volume or less from the viewpoint of fuel efficiency, and 20% by volume. Most preferably: The gasoline of the present invention is not particularly limited as long as it satisfies the properties defined in the present invention except for the FT synthetic base material, and can be produced by any conventionally known method. More than one kind of gasoline base material can be blended. Specifically, for example, straight-run propane fraction centered on propane, straight-run butane fraction centered on butane obtained from crude oil distillation equipment, naphtha reforming equipment, alkylation equipment, etc. Obtained from straight-run desulfurized propane fraction obtained by desulfurization treatment, straight-run desulfurized butane fraction, catalytic cracker, etc. Cracked propane fraction centered on propane / propylene, butane butane Cracked butane fraction, naphtha fraction obtained by atmospheric distillation of crude oil (whole range naphtha), light fraction of naphtha, Naphtha heavy fraction, desulfurized whole range naphtha desulfurized whole range naphtha, desulfurized light naphtha desulfurized light naphtha, desulfurized heavy naphtha desulfurized heavy naphtha, light naphtha converted into isoparaffin by isomerization unit From alkylates obtained by adding (alkylating) lower olefins to hydrocarbons such as isomerized gasoline and isobutane obtained by catalytic conversion, reformed gasoline obtained by catalytic reforming, and reformed gasoline Raffinate, which is a residue extracted from aromatics, Light reformed gasoline, which is a light fraction of reformed ganline, Medium reformed gasoline, which is a medium fraction of reformed gasoline, Medium heavy of reformed gasoline Medium heavy reformed gasoline as a fraction, heavy reformed gasoline as a heavy fraction of reformed gasoline, a mixture of two or more of each reformed gasoline, contact obtained by catalytic cracking method Cracked gasoline (hole range cracked gasoline), light cracked gasoline that is a light fraction of catalytic cracked gasoline, heavy cracked gasoline that is a heavy fraction of catalytic cracked gasoline, hydrocracked gasoline obtained by hydrocracking method, olefin Polymerized gasoline obtained by polymerization of water, olefin fraction obtained by dimerization of propylene or butene, paraffin fraction obtained by hydrogenation of olefin fin fraction obtained by dimerization of propylene or butene, denormalization Examples thereof include paraffin oil, aromatic hydrocarbon compounds (toluene, aromatics having 8 carbon atoms (xylenes), aromatics having 9 carbon atoms, etc.).

The blending amount of these base materials is arbitrary as long as the gasoline of the present invention is adjusted so as to be in the necessary property range, but below, examples of the blending ranges of typical base materials are shown. .

(1) Reformed gasoline: 0 to 80% by volume

(2) cracked gasoline: 0-6 0 capacity ^_0/0

(3) alkylate: 0-4 0 capacity ^_0/0

(4) Isomerization Gasoline: 0-3 0 volume ^_0/0 The gasoline of the present invention may also contain oxygenates.

Examples of the oxygen-containing compound include alcohols having 2 to 4 carbon atoms and ethers having 4 to 8 carbon atoms. Specific oxygen-containing compounds include, for example, ethano monoole, isopropyl alcohol, tert-butyl alcohol, methyl-tert monobutyl ether (MTBΕ) ', ethyl tert-butyl ether (ETBE), Examples thereof include tert-amyl methyl ether (TAME), tert-amyl ether. Of these, ethanol, MTB E, and ETBE are preferred. From the viewpoint of reducing carbon dioxide emissions, it is particularly preferable to use ETB E produced from biomass-derived ethanol and biomass-derived ethanol as raw materials. it can. Methanol is not detected when tested according to the provisions of JISK 2536 “Petroleum products – Ingredients test method” because methanol is corrosive and may increase the concentration of aldehyde in the exhaust gas. % Or less). The oxygen-containing compound content in the gasoline of the present invention is 3.8% by mass or less in terms of oxygen atom from the viewpoint of compatibility with automobile fuel system parts and the suppression of NOx in exhaust gas. Is preferably 3.5% by mass or less, more preferably 2.7% by mass or less, and most preferably 1.3% by mass or less. \ In the present invention, the content (capacity./.) Of all or a part of the distillate of the FT synthesis base material with a distillation range of 25 ° C to 220 ° C is A, and the carbon number is 4-8. The following formulas (1) to (5) are satisfied, where B is the content (volume%) of ethers and B is the content of alcohols having 2 to 4 carbon atoms (volume%): An unleaded gasoline composition with a research octane number of 89.0 or higher, a motor octane number of 80.0 or higher, a 50% distillation temperature of 75 ° C to 110 ° C, and a sulfur content of 10 mass ppm or less An example is a preferred form. .

(1) 50≥ A> 0

(2) B + C> 0

(3) 25≥ B≥ 0

(4) 1 5≥ C≥ 0

(5) A / (B + C) ≥ 1 In other words, the total or partial content (volume%) of the distillate whose FT synthesis base material has a distillation temperature range of 25 ° C to 220 ° C When A is A, it is necessary to satisfy the following (1)

(1) 50≥ A> 0 'This means that the FT synthetic substrate must be contained in the range of 50% by volume or less. If the content of the FT synthetic substrate exceeds 50% by volume, the octane number may decrease and fuel consumption may deteriorate.

Also, when the content (capacity%) of C4-8 ethers is B and the content (capacity%) of C2-4 alcohols is C, the following (2) must be satisfied: There is. .

(2) B + C> 0

This means that it is necessary to contain at least one of ethers having 4 to 8 carbon atoms and alcohols having 2 to 4 carbon atoms. When neither is contained, the effect of improving the octane number by the oxygen-containing compound cannot be obtained. In addition, when the content (volume%) of ethers having 4 to 8 carbon atoms is B, it is necessary to satisfy the following (3). , '

(3) 25≥ B≥ 0

This means that the blending amount of C4-8 ethers needs to be 25% by volume or less. Exceeding 25% by volume of ethers may lead to a reduction in fuel consumption and increase NOx in the exhaust gas. '

In addition, when the content (volume%) of the alcohol having 2 to 4 carbon atoms is C, it is necessary to satisfy the following (4).

(4) 1 5≥C≥ 0

This means that the amount of alcohol having 2 to 4 carbon atoms needs to be 15% by volume or less. If the blending amount of alcohol exceeds 15% by volume, fuel consumption may be reduced, NOx in the exhaust gas may increase, and there may be a problem with the compatibility of automobile fuel system components. .

In addition, the content (volume%) of all or a portion of the FT synthesis base material with a distillation temperature range of 25 to 220 ° C is A, and the content of ethers having 4 to 8 carbon atoms (volume%). When the capacity / ₀ ) is B and the content (volume%) of alcohols having 2 to 4 carbon atoms is C, the following (5) must be satisfied.

(5) A / (B + C) ≥ 1

Equation (5) represents the ratio of the FT synthesis substrate to ethers and alcohols. By satisfying equation (5), the octane number of ethers and alcohols The improvement effect can be maximized. Further, the formula (5) preferably satisfies 1.5 or more, more preferably 2.0 or more. If the value of AZ (B + C) is less than 1, the effect of improving the octane number by ethers and alcohols may be small. 'As the ethers having 4 to 8 carbon atoms, ETBE produced using ethanol derived from biomass as a raw material can be particularly preferably used from the viewpoint of suppressing carbon dioxide emission.

For example, if 95% by volume or more of ethers having 4 to 8 carbon atoms are ETB E produced using biomass-derived ethanol as a raw material, and alcohols having 2 to 4 carbon atoms are less than 0.1% by volume, It is possible to achieve a balanced supply source diversification, octane number improvement effect, and carbon dioxide reduction effect. In this case, if the ETBE content is in the range of 3% by volume or more and 8% by volume or less, it is even more preferable including compatibility with automobile parts.

In addition, as the alcohol having 2 to 4 carbon atoms, biomass-derived ethanol can be particularly preferably used from the viewpoint of suppressing carbon dioxide emission. For example, 95% by volume or more of alcohols having 2 to 4 carbon atoms are ethanol-derived ethanol, and ethers having 4 to 8 carbon atoms are less than 1% by volume. The effect of improving the octane number and the effect of reducing carbon dioxide can be achieved with good balance. In this case, it is particularly preferable that the content of ethanol is in the range of 1% by volume to 3% by volume, including compatibility with automobile parts. The research method octane number (RON) of the gasoline of the present invention needs to be 89.0 or more from the viewpoint of knocking resistance, acceleration, and drivability.

If the gasoline of the present invention are primarily used in regular gasoline specification vehicles, more preferably R ON is 90.0 or more, C0 ₂ emissions during increase of C0 ₂ emissions during gasoline production is running From the viewpoint of exceeding the reduction in the amount, RON is preferably less than 96.0.

On the other hand, when the gasoline of the present invention is mainly used in premium gasoline specification vehicles, in order to maximize performance such as knock resistance, acceleration, and drivability, RO Is preferably 96.0 or more, more preferably 98.0 or more, more preferably 99.5 or more, and even more preferably .10.00 or more. .

In addition, from the viewpoint of preventing deterioration of anti-knocking performance at high speed, the motor method octane number (MON) of the gasoline of the present invention needs to be 80.0 or more.

When the gasoline of the present invention is mainly used in a regular gasoline specification vehicle, the MON is more preferably 81.0 or more, further preferably 81.5 or more, and 82. Even more preferably 0 or more.

On the other hand, when the gasoline of the present invention is mainly used in a premium gasoline specification vehicle, it is preferably 84.0 or more from the viewpoint of preventing deterioration in anti-knock performance at high speed, and 86.0 or more. More preferably, it is more preferably 87.0 or more, even more preferably 87.5 or more, still more preferably 88.0 or more, and 88.5 or more. It is most preferable that

The research method octane number (RON) and the motor method octane number (MON) here mean the research method octane number and the motor method octane number measured by JIS K 2280 “Octane number and cetane number test method”.

The sulfur content of the gasoline of the present invention needs to be 10 mass ppm or less, and preferably 8 mass ppm or less. Further, when the RON of the gasoline of the present invention is 96.0 or more, the sulfur content is more preferably 5 mass ppm or less. ^ If the yellow content exceeds 10 mass p pm, it may adversely affect the performance of the exhaust gas purification treatment catalyst, and the concentration of NO x, CO, HC in the exhaust gas may increase, and the amount of benzene emitted Is also not preferable because it may increase.

The sulfur content here means a value measured according to JI S K 254 1 “Crude oil and petroleum product monosulfur yellow test method”.

The gasoline of the present invention needs to be unleaded. Lead-free refers to the fact that alkyl lead compounds such as tetraethyl lead are not substantially added, even if they contain trace amounts of lead compounds, the content is JISK 225 5 `` It must be less than the lower limit (0 OO lg / 1) of the appropriate classification of “Test method for lead content in gasoline”. Means'. The initial distillation point (IBP) of the gasoline of the present invention is preferably 20 ° C or higher, more preferably 23 ° C or higher. If I BP is less than 20 ° C, hydrocarbons in the exhaust gas may increase. On the other hand, IBP is preferably 37 ° C or lower, more preferably 35 ° C or lower. If I BP exceeds 37 ° C, low-temperature drivability may be reduced.

The 10 vol% distillation temperature (T 10) of the gasoline of the present invention is preferably 35 ° C or higher, more preferably 40 ° C or higher. Τ If 10 is less than 35 ° C, hydrocarbons in the exhaust gas may increase, and vapor lock may reduce high temperature operability. On the other hand, T 10 needs to be 70 ° C or lower, and preferably 60 ° C or lower. If T 10 exceeds 70 ° C, cold startability may be reduced. \

The 30 vol% distillation temperature (T30) of the gasoline of the present invention is preferably 55 ° C or higher, more preferably 60 ° C or higher. If T 3.0. Is less than 55 ° C, fuel consumption may deteriorate. On the other hand, T 30 is preferably 77 ° C or lower, more preferably 75 ° C or lower, and further preferably 70 ° C or lower. If T 30 exceeds 77 ° C, the low-temperature operability may be reduced.

50 capacity ^_0/0 distillation temperature gasoline of the present invention (T 50), from the viewpoint of preventing deterioration of the fuel economy, must be at 75 ° C or higher, preferably not less 80 ° C or higher Yes. On the other hand, from the viewpoint of preventing deterioration in normal temperature drivability, T 50 needs to be 110 ° C or lower, preferably 105 ° C or lower, and more preferably 100 ° C or lower. preferable.

The 70 vol% distillation temperature (T70) of the gasoline of the present invention is preferably 95 ° C or higher. If T70 is less than 95 ° C, the fuel efficiency may deteriorate. On the other hand, T 7,0 is preferably 135 ° C or lower, more preferably 130 ° C or lower. If T70 exceeds 35 ° C, the low-temperature operability during cold operation may decrease, and there will be an increase in hydrocarbons in exhaust gas, an increase in intake pulp deposits, and combustion chamber deposits. May increase.

The 90 vol% distillation temperature (T90) of the gasoline of the present invention is preferably 1 15 ° C or higher, more preferably 120 ° C or higher. If T 90 is less than 1 15 ° C, Fuel consumption may deteriorate. On the other hand, from the viewpoint of preventing deterioration of low temperature and normal temperature operability when cold, increasing dilution of engine oil with gasoline, increasing hydrocarbon exhaust gas, engine oil deterioration and sludge generation, T90 is It is necessary that the temperature is 180 ° C. or less, preferably 1 75 ° C. or less, more preferably 170 ° C. or less, and further preferably 165 ° C. or less.

The distillation end point (E P) of the gasoline of the present invention is preferably 150 ° C. or higher. Further, EP needs to be 220 ° C or lower, preferably 215 ° C or lower, more preferably 200 ° C or lower, and further preferably 195 ° C or lower. If EP exceeds 220 ° C, intake valve deposits may increase combustion chamber deposits and spark plug smoldering may occur.

Here, IBP, T10, T30, Τ50, Τ70, 、 90, and EP mean values (° C) measured by JISK 2254 “Petroleum products ¹ ” Distillation test method ”.

The lead vapor pressure (RVP) of the gasoline of the present invention needs to be 44 kPa or more and 93 kPa or less. The gasoline of the present invention is preferably adjusted according to the season and region where it is used. Specifically, for warm seasons and regions, 44-72 k Pa is preferred, 44-65 k Pa is more preferred, 50-65 k Pa is more preferred, 55-65 k Pa Is most preferred. On the other hand, for cold seasons and regions, 60 to 93 kPa is preferable, 65 to 93 kPa is more preferable, 70 to 93 kPa is more preferable, and 70 to 88 kPa is most preferable. If the RVP is high, malfunctions due to vapor lock may occur, and if the RVP is low, the startability in the cold state may deteriorate. Vapor pressure (RVP) 'here refers to the value (k Pa) measured by JIS K 2258 “Crude oil and fuel oil vapor pressure test method (lead method)”.

Density at 1 5 ° C of gasoline of the present invention, from the viewpoint of suppressing deterioration of the fuel economy, it is preferably 0. 690 gZ cm ³ or more, 0. 700 cm ³ or more der Rukoto more preferably, 0 . even more preferably 71 0 gZ cm ³ or more, and even more preferably from at 0. 715 gZcm ³ or more. Further, when the research octane number of the gasoline of the present invention is 96.0 or more, the density is preferably 0.720 g / cm ³ or more, and more preferably 0.730 _g cm ³ or more. -On the other hand, the density at 15 ° C is preferably 0.78 3 gZ cm ³ or less from the viewpoint of preventing deterioration of acceleration and smoldering of the plug, and 0.770 _{g <} / cm ³ or less. More preferably, 0.760 gZcm ³ or less is even more preferable. Further, when gasoline research octane number of the present invention is less than 96.0 is preferably 0. 7 50 g_ c πι ³ below, 0. 740 _g cm ³ or less is more preferable.

The density at 15 ° C here means the value (g / cm ³ ) measured by JISK 2249 “Density test method for crude oil and petroleum products and density / mass / capacity conversion table”.

The oxidation stability of the gasoline of the present invention needs to be 240 minutes or more, preferably 480 minutes or more, more preferably 960 minutes or more, from the viewpoint of suppressing the formation of gum during storage. Even more preferred is 1440 minutes or more. \

Oxidation stability here means the value (min) measured by JISK2287 “Gasoline oxidation stability test method (induction period method)”.

The gasoline of the present invention needs to have a copper plate corrosion (50 ° C, 3 hours) of 1 or less, and is preferably la. If copper plate corrosion exceeds 1, the fuel system conduit may corrode.

Copper plate corrosion here means the value measured in accordance with JISK 25 1 3 “Petroleum product-copper plate corrosion test method” (test temperature 50 ° C, test time 3 hours). The actual gum amount of the gasoline of the present invention is preferably 5 _mg l 00 ml or less, more preferably 3 mg Z 10 O ml or less, and 1 mg / 100 ml or less. Further preferred. Further, the amount of unwashed actual gum of the gasoline of the present invention is preferably 3 Omg / 10 Om 1 or less, and more preferably 20 mg Z100 m1 or less. Further, when the research octane number of the gasoline of the present invention is less than 9 6..0, the amount of unwashed actual gum is preferably 1 Omg / l O Oml or less, 5 m 10 Oml or less It is more preferable that When the amount of unwashed actual gum and the amount of actual washed gum exceed the above values, there is a concern that precipitates may be generated in the fuel introduction system and the suction pulp may become stuck.

The amount of actual and non-washed real gum here is JISK 226 1 "Petroleum products-Automobile gasoline and aviation fuel oil-Real gum test method-Injection evaporation method" It means the value measured by (mg Z l 0 0 ml).

The benzene content in the gasoline of the present invention must be 1% by volume or less, 0.5 volume. / ₀ or less is preferable. If the benzene content exceeds 1% by volume, the concentration of benzene in the exhaust gas may increase.

The benzene content here means the benzene content (capacity. /.) Measured according to JI S K 2 5 3 6 “Petroleum products – Component test method – Aromatic test method by gas chromatography”.

The amount of kerosene mixed in the gasoline of the present invention is preferably 4% by volume or less. If the amount of kerosene mixed exceeds 4% by volume, engine startability may deteriorate.

Here, the amount of kerosene mixed is determined by the content of normal paraffin hydrocarbons with 1 to 3 and 14 carbon atoms based on the total amount of gasoline, and is in accordance with the provisions of JISK 2 5 3 6 “Method for testing one component of petroleum products”. This means that the conversion value of kerosene obtained is 4% by volume or less.

The aromatic content in the gasoline of the present invention is 45 volumes. / ₀ or less is preferable, 42% by volume or less is more preferable, and 40% by volume or less is more preferable. In addition, when the RON of the gasoline of the present invention is less than 96.0, the aromatic content is preferably 35% by volume or less, more preferably 30% by volume or less, and 25% by volume. % Is even more preferable, and 22% by volume or less is most preferable. If the aromatic content is high, intake valve deposits and combustion chamber deposits may increase and smoldering of spark plugs may occur. The concentration of benzene in the exhaust gas may also increase. On the other hand, the aromatic content is 10 capacity. / ₀ or more is preferred, 15 capacity. / ₀ or more is more preferable, and 18% by volume or more is more preferable. When the RON of the gasoline of the present invention is 96.0 or more, the aromatic content is preferably 25% by volume or more, more preferably 30% by volume or more, and 35% by volume. More preferably, it is at least%. If the aromatic content is low, the fuel consumption may deteriorate.

The aromatic content here means the aromatic content (volume%) in gasoline measured by JIS K 2 5 3 6 “Petroleum product one-component test method—Fluorescent indicator adsorption method”. ·.

The olefin content in the gasoline of the present invention is preferably 35% by volume or less, More preferably, it is 2'5% by volume or less. If the olefin content exceeds 35% by volume, the oxidation stability of gasoline may deteriorate and intake valve deposits may increase.

Here, the olefin component means the olefin content (capacity%) in gasoline measured by 'J I S K 2536 "Petroleum product one-component test method, one fluorescent indicator adsorption method". ·

The gasoline sensitivity of the present invention (difference between RON and MON; RON-MON) is preferably 12.5 or less, more preferably 12.0 or less, and 11.5 or less. More preferably, it is 11.0 or less. Further, when the research octane number of the gasoline of the present invention is less than 96.0, the sensitivity is preferably 10.0 or less, more preferably 9.5 or less, It is more preferably 9.0 or less, and most preferably 8.5 or less. If the sensitivity is small, the knocking resistance at high speed and high engine speed may deteriorate.

The manganese content in the gasoline of the present invention is preferably 2 mass ppm or less, more preferably 1 mass ppm or less. The iron content in the gasoline of the present invention is preferably 2 mass ppm or less, more preferably 1 mass ppm or less. The content of sodium in the gasoline of the present invention is preferably 2 mass ppm or less, and more preferably 1 mass ppm or less. The content of the power rum in the gasoline of the present invention is preferably 2 mass ppm or less, and more preferably 1 mass ppm or less. The phosphorus content in the gasoline of the present invention is preferably 2 mass ppm or less, more preferably 1 mass ppm or less, and even more preferably 0.2 mass ppm or less. If the content of manganese, iron, sodium, potassium, or phosphorus exceeds the above values, the amount of accumulation on the exhaust gas purification catalyst will increase, the catalyst carrier will deteriorate, the air / fuel ratio sensor will deteriorate, etc. May reduce efficiency. The manganese, iron, and sodium contents here are “combustion ashing one inductively coupled plasma emission method”, the potassium content is “combustion ashing one atomic absorption method”, and the phosphorus content is AS TM D 323 1 It is a value measured by “Standard Test Method for Phosphorus in Gasoline”.

In the following, the measurement methods of “combustion ashing inductively coupled plasma emission method” and “combustion ashing single atom absorption method” will be described in detail. ' (1) Take a 20 g sample in a platinum dish. .

(2) Add 0.4 g of powdered sulfur to suppress the volatilization of the component elements, and remove the volatile matter at 150 ° C for 1 hour on a sand path.

(3) Burn the residue. '

(4) Ash for 2 to 3 hours in an electric furnace at 500 ° C.

(5) Dissolve in 2 to 3 mL of concentrated sulfuric acid and make up to 20 mL. .

(6) Manganese, iron, and sodium contents are inductively coupled plasma emission spectrometer (Shimadzu Corporation, ICP S-8000). Phosphorus content is atomic absorption photometer (Hitachi, Ltd., Z 6100) ) To analyze. .

The gasoline of the present invention preferably contains an antioxidant and a metal deactivator for storage stability. Specifically, as antioxidants, N, N'-diisopropyl ^^-p-phenylenediamine, N, N'-diisobutynolone, p-phenylenediamine, and the like, and 2 , 6-di-tert-butyl-4-methylphenol, hindered phenols such as hindered phenols can be used as known compounds as antioxidants such as alkylphenols, and as a metal deactivator, Known compounds can be used as metal deactivators such as amine carbonate condensation compounds such as N, N, -disalicylidene-1,2-diaminopropane. The amount of antioxidant and metal deactivator added is not particularly limited, but the above-mentioned oxidation stability is set to a preferred value, and the amount of unwashed gasoline in the gasoline composition after addition including other additives Is preferably set to the above-mentioned preferable value. Specifically, the antioxidant is preferably 5-10 Omg / 1, more preferably 10-50 mg / l. The metal deactivator is preferably 0.5 to 1 Omg / 1, more preferably 1 to 5 mg / l.

The gasoline of the present invention can contain a clean dispersant to prevent deposits such as intake valves from accumulating. As the detergent dispersant, compounds known as gasoline detergent dispersants such as succinic acid imide, polyalkylamine, and polyetheramine can be used. Among these, it is desirable that there is no residue when pyrolysis is performed at 300 ° C in air. More preferably, polyisoptenylamine and / or polyetheramine are used.

The content of the cleaning dispersant is 25 to 1000 per liter of gasoline of the present invention. m ′ g is preferable, and from the viewpoint of preventing intake pulp deposit and further reducing combustion chamber deposit, 50 to 50 mg is more preferable, and 100 to 300 mg is most preferable. In the case of a cleaning dispersant, an active ingredient that contributes to cleanliness may be diluted with an appropriate solvent. In such a case, the above addition amount means the addition amount as an active ingredient.

The gasoline of the present invention can contain a friction modifier to improve lubricity. The main friction modifiers are, for example, alcohols; alcohol compounds having 1 to 4 hydroxyl groups and having 1 to 30 carbon atoms; carboxylic acids; reaction products of monocarboxylic acids and dallicol or trihydric alcohols. An ester of a hydroxyl group; an ester of a polycarboxylic acid and a polyhydric alcohol;> NR (wherein R is a hydrocarbon group having 5 to 40 carbon atoms; and at least 1 having one or more substituents An ester of a polyhydric alcohol combined with a single nitrogen compound, an amide compound of a carboxylic acid and an alcoholamine, etc. These can be used singly or as a mixture. A hydroxyl group-containing ester which is a reaction product of a monocarboxylic acid having 10 to 25 and a glycol or a trihydric alcohol and / or a carbon having 5 to 25 carbon atoms. An amide compound of boric acid and alcohol amine is more preferable, and an amide of a monocarboxylic acid having 10 to 25 carbon atoms and a glycerin ester and a monocarboxylic acid having 5 or 25 carbon atoms and diethanolamine is used. More preferred are compounds.

The addition amount of the friction modifier is not particularly limited, but it may be added together with other additives so that the unwashed actual gum amount of the gasoline composition after the addition satisfies the above-mentioned preferable range. In addition, from the standpoint that sufficient fuel economy and output improvement effect can be exhibited, while improvement of the effect cannot be expected even if more is added, preferably 10 to 300 mg per liter of gasoline of the present invention, More preferably, it should be added so that the content is 30 to 2500 mg.

In addition, since products that are marketed as friction modifiers may be diluted with an appropriate solvent that contributes to wear resistance, such products are added to the gasoline of the present invention. In some cases, the above addition amounts mean the addition amounts as active ingredients.

Other fuel oil additives that can be added to the gasoline of the present invention include: Surface ignition inhibitors such as organic phosphorus compounds, anti-icing agents such as polyhydric alcohols or ethers thereof, alkali metal salts or alkaline earth metal salts of organic acids, auxiliary alcohols such as higher alcohol sulfates, ayuon surface activity Agents, cationic surfactants, antistatic agents such as amphoteric surfactants, coloring agents such as diazo dyes, organic carboxylic acids or their derivatives, antifungal agents such as alkenyl succinic acid esters, sorbitan esters, etc. Examples include water-removing agents, discriminating agents such as kirizanine and coumarin, and odorants such as natural essential oil synthetic fragrances.

One or more of these additives can be added, and the total addition amount is preferably 0.1% by mass or less based on the total amount of gasoline.

[Industrial applicability]

According to the present invention, a gasoline excellent in exhaust gas purification performance, fuel consumption performance, and drivability can be obtained using an FT synthetic base material.

[Example]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

A Fischer-Tropsch (FT) reaction was applied to a gas mixture containing hydrogen and carbon monoxide as main components to obtain FT synthesis substrate A with a distillation temperature range of 3 ° C to 1 65 ° C. . FT synthetic base A is normal paraffin fraction 7 3. 6 vol%., Isoparafu 'in minute 2. 5% by volume, including Orefin component 2 3. 9 volumes ^_0/0. The FT synthetic base A and 5 vol ^_0/0, reformulated gasoline, catalytically cracked gasoline, alkylate, toluene, gasoline components and antioxidants, such as Bruno Rumarubutan, metal deactivators, detergent dispersants ,, The gasoline composition of Example 1 was prepared by blending a friction modifier. The properties are shown in Table 1.

By hydrorefining the naphtha fraction obtained by applying the FT reaction to a mixed gas containing hydrogen and carbon monoxide as the main components, the distillation temperature range is 35 ° (~ 80 0). ° O? 17 synthetic base material 8 was obtained. 'FT synthetic base material B has a normal paraffin content of 90. Contains 7% by volume and 9.3% by volume of isoparaffin. 6% by volume of this FT synthetic base material B, gasoline base materials such as reformed gasoline, catalytic cracking gasoline, alkylate, toluene, normal butane and antioxidants, metal deactivators, detergent dispersants, friction A gasoline composition of Example 2 was prepared by blending a conditioner, whose properties are shown in Table 1.

<Example 3> +

Side reaction product when hydrotreating middle distillate from 150 ° C to 360 ° C obtained by applying FT reaction to mixed gas containing hydrogen and carbon monoxide as main components As a naphtha, an FT synthesis substrate C having a distillation temperature range of 35 ° C. to 1 65 ° C. was obtained. FT synthetic base C is normal paraffin component 5 9. 1/6 volume ^_0/0, including isoparaffins fraction 4 0. 4 Capacity%. This FT synthesis base material C is 6% by volume, gasoline base such as reformed gasoline, catalytic cracking gasoline, alkylate, toluene, solmal butane, antioxidant, metal deactivator, detergent dispersant, friction adjustment. The gasoline composition of Example 3 was prepared by blending the agent. Its properties are shown in Table 1.

Example 4>

By hydrocracking the FT wax obtained by applying the FT reaction to a mixed gas containing hydrogen and carbon monoxide as the main components, the distillation temperature range is 35 ° C to 1 65 ° C. FT synthetic substrate D was obtained. FT Synthetic substrate D contains 22.1% by volume of normal paraffin and 77.9% by volume of isoparaffin. 7% by volume of this FT synthetic base D, gasoline base such as reformed gasoline, catalytic cracking gasoline, phenolic chelate, toluene, normal butane and antioxidants, metal deactivator, detergent dispersant, friction adjustment The gasoline composition of Example 4 was prepared by blending the agent. The properties are shown in Table 1.

FT synthetic substrate D 32% by volume, gasoline substrate such as reformed gasoline, catalytic cracking gasoline, alkylate, toluene, normal butane and antioxidants, metal deactivator, detergent dispersant, friction adjustment A gasoline composition of Comparative Example 1 was prepared by adding an antioxidant. The properties are shown in Table 1.

Comparative Example 2>

As Comparative Example 2, commercially available premium gasoline was used. The properties are shown in Table 1. Example 5>

10% by volume of FT synthetic base material A used in Example 1, gasoline base materials such as reformed gasoline, catalytic cracking gasoline, alkylate, toluene, normal butane, and antioxidants and metal inertness The gasoline composition of Example 5 was prepared by blending the agent. The properties are shown in Table 2.

Example 6>

12% by volume of the FT synthetic substrate B used in Example 2 and gasoline substrates such as reformed gasoline, catalytic cracking gasoline, alkylate, toluene, and normal butane, and antioxidants and metal additives. The gasoline composition of Example 6 was prepared by blending the activator. The properties are shown in Table 2.

15% by volume of FT synthetic substrate C used in Example 3, gasoline substrates such as reformed gasoline, catalytic cracking gasoline, alkylate, toluene, normal butane, and antioxidants and metal deactivators Was added to prepare the gasoline composition of Example 7. The properties are shown in Table 2.

<Example 8>.

20% by volume of FT synthetic substrate D used in Example 4, gasoline substrates such as reformed gasoline, catalytic cracking gasoline, alkylate, toluene, normal butane, and antioxidants and metal deactivators Was added to prepare the gasoline composition of Example 8. The properties are shown in Table 2.

Also, 10 volumes of FT synthetic substrate D. Preparation / _0, reformulated gasoline, catalytically cracked gasoline, Ryo Rukireto, toluene, by blending the gasoline base material and antioxidants such as n-butane and metal deactivator, a gasoline composition of Example 9 did. The properties are shown in Table 2.

The FT synthetic base D 5 5 capacity ^_0/0, reformulated gasoline, catalytically cracked gasoline, alkylate over preparative, by blending toluene, quotas gasoline components and antioxidants, such as butane and metal deactivators A gasoline composition of Comparative Example 3 was prepared. The properties are shown in Table 2. ' Comparison Example 4>.

As Comparative Example 4, commercially available regular gasoline was used. The properties are shown in Table 2. <Example 10>

By hydrotreating a naphtha fraction obtained by applying a Fischer-Tropsch (FT) reaction to a mixed gas containing hydrogen and carbon monoxide as main components, a distillation temperature range of 35 ° C to 80 ° C is obtained. An FT synthetic substrate X at ° C was obtained. 15 volumes of this FT synthetic substrate X. 7% by volume of ethyl acetate butyl ether (ETB E) manufactured from ethanol derived from biomass / ₀ and biomass and blended with gasoline base materials derived from crude oil such as reformed gasoline, catalytic cracking gasoline and alkylate The gasoline composition of Example 10 was prepared. The properties are shown in Table 3.

<Example 1 1>-When hydrotreating a middle distillate of 150 ° C to 360 ° C obtained by applying the FT reaction to a mixed gas containing hydrogen and carbon monoxide as main components As a side reaction product naphtha, an FT synthesis substrate Y having a distillation temperature range of 35 ° C to 16.5 ° C was obtained. This FT synthetic base material Y is mixed with 15% by volume and 7% by volume of ETBE made from biomass-derived ethanol as a raw material, and gasoline bases derived from crude oil such as reformed gasoline, catalytic cracking gasoline and alkylate. Thus, the gasoline composition of Example 11 was prepared. The properties are shown in Table 3.

By hydrocracking the FT wax obtained by applying the FT reaction to a mixed gas mainly composed of hydrogen and carbon monoxide, an FT with a distillation temperature range of .35 ° C to 165 ° C. A synthetic substrate Z was obtained. This FT synthetic base material Z is made from 15% by volume and 7% by volume of ETBE made from biomass-derived ethanol, and blended with base materials derived from crude oil such as reformed gasoline, catalytic cracking gasoline and alkylate. Thus, the gasoline composition of Example 12 was prepared. The properties are shown in Table 3.

The FT synthetic base Z of ETBE 7 volume ^_0/0 that produce ethanol from 10% by volume and biomass as raw material, reformulated gasoline, catalytically cracked gasoline, blending the gasoline base material derived from crude oil, such as Arukire bets Thus, the gasoline composition of Example 13 was prepared. The properties are shown in Table 3. Example 1 4>

By blending 7% by volume of FT synthetic substrate X and 3% by volume of ethanol derived from biomass, and a gasoline substrate derived from crude oil such as reformed gasoline, catalytic cracking gasoline, alkylate, etc., the gasoline of Example 14 A composition was prepared. The properties are shown in Table 3.

Example 1 5>

Example 1 5 By blending 7% by volume of FT synthetic base material and 3% by volume of ethanol derived from biomass, and a base material derived from crude oil such as reformed gasoline, catalytic cracking gasoline, and alkylate. A gasoline composition was prepared. The properties are shown in Table 3.

Example 1 6>-

By blending 7% by volume of FT synthetic base Z with 3% by volume of ethanol from pi-pimas and a base of gasoline derived from crude oil such as reformed gasoline, catalytic cracking gasoline, alkylate, etc. A gasoline composition was prepared. The properties are shown in Table 3.

<Example 1 7>.

5% by volume of FT synthetic substrate Z and 3 volumes of ethanol derived from biomass. The gasoline composition of Example 17 was prepared by blending a gasoline base derived from crude oil such as reformed gasoline, catalytic cracking gasoline, alkylate or the like. The properties are shown in Table 3.

Comparative Example 5>

7 volumes of ETBE made from biomass-derived ethanol as raw material for commercial premium gasoline. The gasoline composition of Comparative Example 5 was prepared by mixing / ₀ . The properties are shown in Table 3.

Ku Haku Comparative Example 6>

The gasoline composition of Comparative Example 6 was prepared by mixing 3% by volume of biomass-derived ethanol with commercial premium gasoline. The properties are shown in Table 3.

(Property measurement)

The properties of the base material and the properties of the test gasoline in the examples and comparative examples are as follows. Measured.

The research octane number and the motor octane number are J I S K 2 2 8 0

The values are based on the research octane number and the motor octane number measured by the “Octane number and cetane number test method”.

Sulfur content was measured by J I S K 2 5 4 1 “Method for testing sulfur content in crude oil and petroleum products”.

Lead content was measured by J I S K 2 2 5 5 “Test method for lead content in gasoline”. Distillation properties (I B P, T 10, Τ 3.0, Τ 50, Τ 70, Τ 90, Ε Ρ) were all measured by J I S K 2 254 “Petroleum products—distillation test method—atmospheric pressure method”. Vapor pressure (@ 37.8 ° C) was measured by J I S K 2 2 5 8 “Crude oil and fuel oil vapor pressure test method (Lead method)”.

The density (@ 15 ° C) was measured by J I S,. K 2 24 9 “Density test method for crude oil and petroleum products and density, mass, capacity conversion table”.

Oxidation stability was measured by J I S K 2 2 8 7. “Gasoline Oxidation Stability Test Method (Induction Period Method)”.

Copper plate corrosion was measured according to JI S K 2 5 1 3 “Petroleum products—copper plate corrosion test method” (test temperature 50 ° C., test time 3 hours).

The amount of unwashed and washed actual gum was measured by J I S K 2 2 6 1 “Petroleum products—Automobile gasoline and aviation fuel oil—Real gum test method—Injection evaporation method”. ..

Benzene was measured by J I S Κ 2 5 3 6 “Petroleum product one-component test method — Gasoline aromatic test method”.

Aromatic content and olefin content were measured by JI S K 2 5 3 6 “Petroleum products—component test method, one fluorescent indicator adsorption method”.

Kerosene content was measured in accordance with J I S K 2 5 3 6 “Petroleum product one-component test method”.

Manganese, iron, and sodium contents are “combustion ashing—inductively coupled plasma emission method”, potassium content is “combustion ashing—atomic absorption method”, and phosphorus content is AS TM D 3 2 31 “Standard Test It was measured by “Method for Phosphorus in Gasoline”. (Gasoline supply source diversification index)

For the gasolines of Examples 1 to 9 and Comparative Examples 1 to 4, the blending ratio of the base material that can be used as a raw material other than crude oil from the blending amount of the FT synthetic base material and the blending amount of the gasoline base material using crude oil as the raw material Demanded diversification indicators for supply sources. The results are shown in Tables 4-5.

(Acceleration performance evaluation)

Acceleration performance was evaluated using the following test vehicle on a chassis dynamometer maintained at an environmental temperature of 25 ° C and an environmental humidity of 50%. In the test, after fully warming up the test vehicle, in the D range (OD is on), full open acceleration from 50 kmZh to 11 km "h is performed 10 times from 60 km / h to 100 kh. The time required to reach the target was measured, and the average of the seven required times excluding the first three was defined as the acceleration time Note that the gasoline in Examples 1-4 and Comparative Examples 1-2 Test vehicle A was used for gasoline in Examples 5 to 9 and Comparative Examples 1 and 2, and test vehicle B was used.

[Test vehicle A]

Engine: Inline 4 cylinder (Premium gasoline specification, with turbocharger)

Displacement: 1 998 c c

Injection method: Multi point type '.

Mission: Automatic Transmission

Exhaust gas purification system: three-way catalyst, air-fuel ratio feed pack control

Compliant with 1990 exhaust gas regulations

[Test vehicle B]

Engine: Inline 4 cylinder (regular gasoline specification)

Displacement: 1498 c c

Injection method: Multi point type

Mission: Automatic transmission

Compliant with 1990 exhaust gas regulations

(Exhaust gas test)

In the exhaust gas test, the emissions of CO and NO X contained in the exhaust gas were measured using the above-mentioned test vehicle in accordance with the technical guidelines for gasoline vehicles by the Ministry of Land, Infrastructure, Transport and Tourism. . (Fuel consumption test). The fuel consumption test uses the above test vehicle and is a gasoline vehicle by the Ministry of Land, Infrastructure, Transport and Tourism.

10-1 Measured according to the 5 mode fuel consumption test method. As shown in Tables 4 to 5, the gasolines of the present invention (Examples 1 to 9) contain a base material derived from FT synthesis, thereby diversifying the supply source, as well as good acceleration performance and low exhaust gas. It can be seen that (CO, NOx) level and good fuel efficiency can be realized. .

(Plending Research Octane Number)

For the gasolines of Examples 10 to 17 and Comparative Examples 5 to 6, the octane number (RON) of the research method of base gasoline not mixed with ethers and alcohols was measured, and the ETB E given by the following formula was calculated. We asked for the Pending RON. The results are shown in Table 6.

Pending RON.

= RON (BASE) + ((RON (OXY)-RON (BASE)) / VOL (OXY)) X 100 where RON (BASE) is the base gasoline RON and RON. (OXY) is the alcohol type , RON after mixing ters, and VOL (OXY) represents the mixing amount (capacity./.) Of alcohols and ethers.

In all of Examples 10 to 17, diversification of gasoline supply sources is achieved by containing an FT synthetic substrate and biomass-derived ETB E or ethanol. .

In addition, Table 6 shows that ETB E's blending RON of Examples 10 to 13 is larger than that of Comparative Example 5, and that the effect of improving the octane number of ETB E is increased by blending the FT synthetic substrate. . Further, the ethanol blending RON of Examples 14 to 17 was larger than that of Comparative Example 6, and it was found that the effect of improving the octane number was increased by blending the FT synthesis base material. table 1

Table 2

Table 3

Table 4

Table 5

Table 6

Example 14 Example 15 Example 16 Example 17 Comparative Example 6

RON (OXY) 90.1 100.1 100.1 100.0 100.1

RON (BASE) 88.3 99.1 99.0 99.2 99.5

VO (OXY) 3 3 3 3 3 Blending RON 148.3, 132.4 135.7 125.9 1 19.5

Claims

The scope of the claims

1. The distillation temperature range of the FT synthesis base material contains all or part of the fraction from 25 ° C to 220 ° C, the LISA method octane number is 89.0 or more, and the motor method octane number is An unleaded gasoline composition characterized by having an 80.degree. C. or higher, 50% distillation temperature of 75.degree. C. or higher and 110.degree. C. or lower, and a sulfur content of 10 mass ppm or less.

2. FT synthesis base material contains all or part of the distillate whose temperature range is 25 ° C to 220 ° C, and the research octane number is 96.0 or more. Is 84.0 or more, Sulfur content is 10 mass ppm or less, 10% distillation temperature is 70 ° C or less, 50% distillation temperature is 75 ° C or more 1 10 ° C or less, 90% distillation temperature is 1 80 ° C or less, distillation end point 220 ° C or less, lead vapor pressure 44 k Pa to 93 k Pa, density (15 ° C) 0. \ 690 _§ /. 111 ³ or more 0.783 g / cm ³ or less, oxidation stability is 240 minutes or more, copper plate corrosion (50 ° C, 3 hours) is 1 or less, cleaning actual gum is 5 mg / l 00ml or less, unwashed actual gum 2. The unleaded gasoline composition according to claim 1, wherein the composition is 3 Omg / l O Oml or less, and the benzene content is 1% by volume or less. .

3. The distillation temperature range of the FT synthesis base material contains all or part of the fraction from 25 ° C to 220 ° C, the research method octane number is 89.0 or more and less than 96.0, the motor method octane number 80.0 or more, sulfur content 10 mass p pm or less, 10% distillation temperature 70 ° C or less, 50% distillation temperature 75 ° C or more 1 10 ° C or less, 90% distillation temperature 180 ° C or less, distillation end point 220 ° C or less, Reed vapor pressure 44 k Pa or more 93 k Pa or less, density (15 ° C) 0.690 g cm ³ or more 0.783 g / cm ³ or less, oxidation stability 240 minutes or more, copper plate corrosion (50 ° C, 3 hours) 1 or less, washed real gum 5 mg / 100 m 1 or less, unwashed real gum 30 mg / 100 m 1 The unleaded gasoline composition according to claim 1, wherein the benzene content is 1% by volume or less.

4. FT synthesis base material with a distillation temperature range of 25 ° C to 220 ° C or a part of the content (volume%) of A and ethers with 4 to 8 carbon atoms When the amount (volume%) is B and the content (volume%) of alcohols having 2 to 4 carbon atoms is C, the following formulas (1) to (5) are satisfied, and the research method octane number is 89. 0 or more, The lead-free lead according to claim 1, characterized in that the motor method octane number is 80.0 or more, the 50% distillation temperature is 75 ° C or more and 1 10 ° C or less, and the sulfur content is 10 mass ppm or less. Gasoline composition.

(1) 50≥ A> 0 '

(2) B + C> 0

(3) 25≥B≥ 0

(4) 1 5≥ C≥ 0

(5) A / (B + C) ≥ 1

5. The lead-free gasoline composition according to any one of claims 1 to 4, wherein the normal paraffin content in the FT synthetic base contained in gasoline is 75% by volume or less. -

6. The lead-free gasoline composition according to any one of claims 1 to 4, wherein the content of isoparaffin in the FT synthetic substrate contained in gasoline is 20% by volume or more. ,

7. The unleaded gasoline composition according to any one of claims 1 to 4, wherein an olefin content in the FT synthetic base contained in gasoline is 5% by volume or more.

8. The content of the FT synthetic base material consisting of all or part of the fraction at the distillation temperature range of 25 to 220 ° C is 3% by volume or more and 30% by volume or less with respect to the total amount of gasoline. The unleaded gasoline composition according to claim 2, wherein:

9. The content of FT synthetic base material consisting of all or part of the distillate with a distillation temperature range of 25 ° C to 220 ° C is 3% by volume to 50% of the total amount of gasoline. The unleaded gasoline composition according to claim 3, wherein the unleaded gasoline composition is / ₀ or less.

10. The unleaded gasoline composition according to any one of claims 1 to 4, which does not contain kerosene.

1 1. Aromatic content is 10% to 45%. /. The unleaded gasoline composition according to claim 2, wherein:

1 2. Aromatic content is 10 volumes. The unleaded gasoline composition according to claim 3, wherein the composition is / ₀ or more and 35% by volume or less.

1 3. Claim that the olefin content is 35% by volume or less Item ':! The unleaded gasoline composition in any one of -4.

1 4. The unleaded gasoline composition according to claim 2, wherein the sensitivity is 12.5 or less. '

1 5. The unleaded gasoline composition according to claim 3, wherein the sensitivity is 10.0 or less.

1 6. Manganese content is 2 mass ppm or less, iron content is 2 mass ppm or less, sodium content is 2 mass ppm or less, potassium content is 2 mass ppm or less, and phosphorus content The unleaded gasoline composition according to any one of claims 1 to 4, characterized in that is 2 mass. P pm or less.

1 7. The unleaded gasoline composition according to any one of claims 1 to 4, comprising an antioxidant and a metal deactivator.

1 8. The lead-free gasoline composition according to claim 2, further comprising a cleaning dispersant.

1 9. The lead-free gasoline composition according to claim 2, further comprising a friction modifier.

20. More than 95% by volume of ethers having 4 to 8 carbon atoms are ethyl acetate butyl ether produced from biomass-derived ethanol, and alcohols having 2 to 4 carbon atoms are less than 0.1% by volume. The unleaded gasoline composition according to claim 4, wherein the unleaded gasoline composition is present.

21. The unleaded gasoline composition according to claim 20, wherein the content of ethyl tertiary butyl ether is 3% by volume or more and 8% by volume or less.

22. More than 95% by volume of alcohols with 2 to 4 carbon atoms are ethanol derived from biomass, and ethers with 4 to 8 carbon atoms are 0.1 volumes. The unleaded gasoline composition according to claim 4, wherein the composition is less than ₀ .

23. The unleaded gasoline composition according to claim 22, wherein the ethanol content is 1% by volume or more and 3% by volume or less.