JP2007153936A - Gasoline - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide gasoline which contains a biomass-derived base from the viewpoint of regenerability and global worming prevention and is excellent in the easiness of exhaust gas cleaning, fuel consumption, and engine operation performance. <P>SOLUTION: Provided is gasoline which has a research octane number of 96.0 or higher and a sulfur content of 10 mass ppm or lower and is characterized by containing a base at least partially consisting of a fraction obtained by treating a feedstock oil mixed with biomass or with biomass and a mineral oil by fluidized catalytic cracking and having a distillation temperature range of from 25 to 220°C. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to gasoline as a fuel for automobiles, and more particularly to gasoline that contains a biomass-derived base material from the viewpoint of renewable and prevention of global warming, and has excellent exhaust gas purification performance, fuel consumption performance, and driving performance.

Conventionally, gasoline is produced by blending one or more kinds of base materials of a gasoline fraction obtained by treating crude oil with various refining apparatuses such as a catalytic reforming apparatus and a catalytic cracking apparatus ( For example, refer nonpatent literature 1.).
Biomass-derived base materials that can be blended with gasoline include ethanol (biomass-derived ethanol) produced by fermenting sugar-based sugar components such as sugarcane and corn in yeast (ethanol derived from biomass), and ethanol and oil production from this biomass ETBE produced by reacting with isobutylene obtained by separation from mixed butylene generated from a fluid catalytic cracker (FCC) or the like in a steam plant or a steam cracker (steam cracker) in an ethylene plant is known (for example, Non-patent document 2).
On the other hand, use of a fatty acid alkyl ester mixture made from natural animal and vegetable oils and fats as a fuel for diesel automobiles is being considered alone or mixed with existing light oil or the like (see, for example, Non-Patent Document 3). ).
Fuel Association, “New Edition Fuel Handbook”, Corona, March 1974, p. 264-267 Handout 3 of the 3rd Renewable Fuel Promotion Conference (October 10, 2003), Ministry of the Environment Central Environmental Council 7th report, July 29, 2003

In recent years, 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 suppressing global warming. Although the amount of harmful substances in the exhaust gas is extremely low, reduction of CO ₂ emissions by improving thermal efficiency, improving fuel efficiency, and the like has been an issue. In the medium to long term, there is a demand for building sustainable mobility.
Under such circumstances, the use of biomass-derived fuel, which can suppress an increase in CO _{2 in} the life cycle and is also renewable energy, is attracting attention as a fuel for gasoline automobiles.
Animal and vegetable fats and oils, which are biomass, have been studied for use as fuel for diesel vehicles by fatty acid methyl esterification. However, since gasoline engines and diesel engines have different ignition characteristics and fraction ranges required for fuel, it is difficult to use these fatty acid methyl esters derived from animal and vegetable oils as fuel for gasoline automobiles.

  As a result of diligent research to solve the above problems, the present inventors have made it possible to use biomass such as animal and vegetable oils and fats in a fluid catalytic cracking apparatus, and make the gasoline have specific properties. Thus, it has been found that excellent exhaust gas purification performance, fuel efficiency performance, and driving performance of gasoline automobiles can be derived, and the present invention has been completed.

  That is, the present invention comprises all or part of a fraction having a distillation temperature range of 25 ° C. to 220 ° C. obtained by treating biomass or a raw material oil mixed with biomass and mineral oil by fluid catalytic cracking. The present invention relates to a gasoline having a research octane number of 96.0 or more and a sulfur content of 10 mass ppm or less.

Hereinafter, the present invention will be described in detail.
The gasoline of this invention needs to contain the base material obtained by processing biomass or the raw material oil which mixed biomass and mineral oil by fluid catalytic cracking (FCC).
Examples of biomass used in the present invention include plant or animal-derived fats and oils. These are esters of higher fatty acids and glycerin, and examples thereof include vegetable oils such as palm oil, rapeseed oil, corn oil, soybean oil, and grape seed oil, and animal oils such as lard. In the case of the present invention, these fats and oils may be used waste oil. Moreover, in the case of this invention, these fats and oils may be 1 type, or 2 or more types of mixtures may be sufficient as them.

  In the fluid catalytic cracking for obtaining the base material contained in the gasoline of the present invention, biomass and mineral oil can be mixed to obtain a raw material oil. These mineral oils include atmospheric residual oil obtained by distilling crude oil, vacuum gas oil obtained by further distillation of atmospheric residue under reduced pressure, vacuum residue, hydrotreated oil, or pyrolysis oil, and Of the mixture. Of these, normal pressure residual oil, vacuum residual oil, and hydrides thereof are referred to as residual oil in the present invention, and the numerical value representing the ratio of these residual oils in the raw oil of the fluid catalytic cracking unit is expressed in weight ratio. It is called ratio (% by weight). The residual oil ratio in the present invention can be freely selected between 0 and 100% by weight.

In the present invention, it is preferable to use a fluid catalytic cracking reactor having a regeneration zone, a reaction zone, a separation zone, a stripping zone and a product recovery zone, the reaction zone outlet temperature is 480 to 540 ° C., and the catalyst / oil ratio is 4 to 12 wt / wt, the reaction pressure is 1 to 3 kg / cm ² G (98 to 294 kPa gauge pressure), the contact time between the feedstock and the catalyst is 1 to 3 seconds, and the ultrastable Y-type zeolite contains 10 to 50% by mass. It is preferable to use a catalyst. The bottom temperature of the distillation column included in the product recovery zone is preferably 380 ° C. or lower.

  In the fluid catalytic cracking in the present invention, the above heavy feedstock such as biomass and mineral oil is continuously brought into contact with the fluidized catalyst, and the heavy feedstock is mainly composed of gasoline or light olefin. An operation that decomposes into light hydrocarbons. For this contact, so-called riser cracking is often used in which both catalyst particles and raw material oil rise in the pipe. The mixture of the product, unreacted product, and catalyst that have undergone catalytic cracking in this way is separated in the separation zone. As the separation zone, a gas-solid separation device using a centrifugal force including a cyclone is preferably used. The separated catalyst is sent to a stripping zone, and most of hydrocarbons such as products and unreacted substances are removed from the catalyst particles. On the other hand, the mixed gas of the product and the unreacted material is sent to a product recovery facility described later. During the reaction, part of the raw material becomes heavier carbonaceous and adheres on the catalyst. The coke in the present invention refers to the carbonaceous material. The catalyst to which coke and partially heavy hydrocarbons are attached is sent from the stripping zone to the regeneration zone (regeneration tower). In the regeneration zone, oxidation treatment of the catalyst to which the coke and the like are attached is performed. The catalyst subjected to this oxidation treatment is a regenerated catalyst, and the coke and heavy hydrocarbons deposited on the catalyst are reduced by combustion. This regenerated catalyst is continuously circulated through the reaction zone. In some cases, the decomposition products are quenched immediately before or after the separator to prevent unnecessary thermal decomposition or over decomposition. The catalyst is heated by the amount of heat generated by the combustion of the carbonaceous material in the regeneration zone, and the heat is brought into the reaction zone together with the catalyst. The heating and vaporization of the raw material oil is performed by this amount of heat. Further, since the decomposition reaction is an endothermic reaction, the amount of heat is also used as the heat of decomposition reaction. Thus, balancing the heat generation in the regeneration zone and the heat absorption in the reaction zone is an essential condition for FCC operation.

As a countermeasure when the heat becomes excessive, there is a method of cooling the catalyst. In this method, a part of the catalyst in the regeneration zone is extracted, and this heat is used for generating steam to take away the heat of the catalyst.
As another countermeasure against excess heat, there is a method of operating in an oxygen-deficient atmosphere with the regeneration zone having two stages and the first stage. In this case, the coke is incompletely burned, and carbon monoxide is discharged as exhaust gas. Excess heat can be discharged out of the system by the difference between the reaction heat when carbon is oxidized to carbon monoxide and the reaction heat when carbon is oxidized to carbon dioxide. The reaction heat (combustion heat) related to the combustion of coke is as follows.
The carbon monoxide discharged out of the system can be further oxidized to carbon dioxide, and the energy can be recovered in the form of electric power or steam.
H ₂ + 1 / 2O ₂ → H ₂ O 12.1 × 10 ⁴ kJ / kg (28900kcal / kg)
C + 1 / 2O ₂ → CO 0.9 × 10 ⁴ kJ / kg (2200kcal / kg)
C + O ₂ → CO ₂ 3.3 × 10 ⁴ kJ / kg (7820 kcal / kg)

  In the present invention, the reaction zone outlet temperature in fluid catalytic cracking is the outlet temperature of the fluidized bed reactor, and is the temperature before the decomposition product is quenched or separated from the catalyst. The reaction zone outlet temperature is preferably 480 to 540 ° C, more preferably 490 to 520 ° C, and further preferably 500 to 510 ° C. If the temperature is lower than 480 ° C., the target products such as gasoline and light olefin cannot be obtained in a high yield, and if the temperature is higher than 540 ° C., thermal decomposition becomes remarkable and the amount of dry gas generated increases, which is not preferable.

  In the present invention, the catalyst / oil ratio in fluid catalytic cracking is the ratio of the catalyst circulation rate (ton / h) and the feed oil supply rate (ton / h), and this catalyst / oil ratio is preferably 4 to 12 wt / h. wt, more preferably 5 to 10 wt / wt, still more preferably 6 to 8 wt / wt. When the catalyst / oil ratio is less than 4, a sufficient decomposition rate cannot be obtained. Further, the amount of heat in the reaction zone is insufficient, or the temperature of the regeneration zone becomes too high, and it is necessary to change the design temperature of the regeneration zone. This is because the catalyst also acts as a heat medium that carries heat from the regeneration zone to the reaction zone. If the catalyst / oil ratio is simply lowered, the amount of heat in the reaction zone becomes insufficient, and the catalyst / oil ratio is lowered. This is because if the reaction zone temperature is maintained, the regeneration zone temperature is increased. On the other hand, when the catalyst / oil ratio is larger than 12, the amount of catalyst circulation becomes large, the catalyst residence time necessary for catalyst regeneration in the regeneration zone cannot be secured, and the catalyst regeneration is not sufficiently performed, which is not preferable.

In the present invention, the reaction pressure in fluid catalytic cracking is the total pressure of the fluidized bed reactor. This reaction pressure is preferably 1 to 3 kg / cm ² G (98 to 294 kPa gauge pressure), more preferably 1.2 to ² kg / cm ² G (118 to 1964 kPa gauge pressure). If it is smaller than 1 kg / cm ² G (98 kPa gauge pressure), the difference from the atmospheric pressure becomes too small, and it becomes difficult to adjust the pressure by the control valve. Further, if the pressure is smaller than 1 kg / cm ² G (98 kPa gauge pressure), the pressure in the regeneration zone also decreases accordingly, and the residence time of the gas necessary for regeneration is secured, so that the container becomes large and economically undesirable. . When the reaction pressure is higher than 3 kg / cm ² G (294 kPa gauge pressure), the ratio of a bimolecular reaction such as a hydrogen transfer reaction to a decomposition reaction that is a unimolecular reaction increases, which is not preferable. The hydrogen transfer reaction here is a reaction in which olefins receive hydrogen from naphthene and turn into paraffin, and it is economically undesirable because it reduces the target light olefin or lowers the octane number of the gasoline fraction. It is a reaction.

  In the present invention, the contact time between the feedstock and the catalyst in fluid catalytic cracking is the time from the contact between the feedstock and the catalyst at the inlet of the fluidized bed reactor until the reaction product and the catalyst are separated at the outlet of the reactor. Say time. The contact time in the present invention is preferably 1 to 3 seconds, more preferably 1 to 2 seconds.

In the present invention, the coke yield in fluid catalytic cracking is the amount of coke produced per feedstock and is expressed in weight%. The coke yield is preferably 4 to 12% by weight, more preferably 5 to 10% by weight, and further preferably 6 to 8% by weight. When the coke yield is less than 4% by weight, the heat required for the reaction is insufficient. When the coke yield exceeds 12% by weight, the amount of heat generated in the regeneration zone becomes too large, which is not preferable because it is subject to operating restrictions such as a reduction in decomposition rate and a decrease in oil passage.
The upper limit value of the coke amount is almost determined for each FCC apparatus. That is, first, the allowable value of coke is determined by the amount of heat that can be discharged out of the system by the above-described countermeasure for excess heat. Further, there is a case where an upper limit value of the amount of CO ₂ discharged is determined depending on the location of the FCC, and the allowable value of coke is limited by the numerical value. Normally, FCC is operated with as much oil flow as possible and as high a cracking rate as possible, and as a result, it is usual to operate at the upper limit of coke.

  In the present invention, in the fluid catalytic cracking, the flow rate of the catalyst and oil introduced into the fluidized bed reactor is expressed by weight ratio. This catalyst / oil ratio is preferably 4-12 wt / wt, more preferably 5-9. A catalyst / oil ratio of less than 4 is not preferable because the amount of heat in the reaction zone is insufficient, or the temperature of the regeneration zone becomes too high, and the design temperature of the regeneration zone needs to be changed. This is because the catalyst also acts as a heat medium that carries heat from the regeneration zone to the reaction zone. If the catalyst / oil ratio is simply lowered, the amount of heat in the reaction zone becomes insufficient, and the catalyst / oil ratio is lowered. This is because if the reaction zone temperature is maintained, the regeneration zone temperature is increased. A catalyst / oil ratio greater than 12 is not preferred because the regeneration zone temperature is lowered, the coke combustion rate is lowered, and catalyst regeneration is not sufficiently performed.

In the present invention, the catalyst used in fluid catalytic cracking is a zeolite which is the main active ingredient, a matrix which is a secondary active ingredient and capable of decomposing large molecules of heavy oil, and a filler obtained by molding a filler such as kaolin with a binder. It is preferable to use it. The main component of the zeolite is ultrastable Y-type zeolite, and the content thereof is preferably 10 to 50% by mass, more preferably 15 to 40% by mass in the catalyst. The catalyst is formed into fine particles having an average particle size of 50 to 90 μm. The bulk density of the catalyst is 0.6 to 0.9 g / cm ³ . The catalyst preferably has a surface area of 50 to 350 m ² / g and a pore volume of 0.05 to 0.5 ml / g.

  In the present invention, the catalyst used for fluid catalytic cracking may include, in addition to ultrastable Y-type zeolite, crystalline aluminosilicate zeolite or silicoaluminophosphate (SAPO) having a pore size smaller than that of Y-type zeolite. Examples of such zeolite or SAPO include ZSM-5, β, omega, SAPO-5, SAPO-11, and SAPO-34. These zeolite or SAPO may be contained in the same catalyst particles as the catalyst containing the ultrastable Y-type zeolite, or may be separate particles.

  In the present invention, the fluid catalytic cracking apparatus is preferably provided with a product recovery facility for separating and recovering the product by its boiling point or the like. The product recovery equipment includes a plurality of distillation towers, absorption towers, compressors, strippers, heat exchangers and the like. The product from 480 to 540 ° C. obtained from the reaction zone is sent to the first distillation column. Here, the heat of the product is removed by a heat exchanger, and a light oil fraction and a heavier fraction are extracted from the bottom of the column, and a gasoline fraction and a lighter fraction are extracted from the top of the column. The light oil fraction can be extracted from the middle stage of the distillation column, and only heavy oil can be extracted from the bottom of the column. Light components obtained from the first distillation column are sent to a compressor to be compressed. Then, it is separated and recovered into gasoline, C4 fraction, C3 fraction and dry gas through a plurality of absorption towers and distillation towers. The C4 fraction here refers to butane and butylene, which are hydrocarbons having 4 carbon atoms. The C3 fraction here refers to propane and propylene which are hydrocarbons having 3 carbon atoms. The dry gas here refers to a hydrocarbon having 2 carbon atoms such as hydrogen, methane, ethane, and ethylene and a gas having a smaller molecular weight than that. Depending on the capability of the distillation tower, a part of the C4 fraction may be mixed with gasoline, or a part of the C4 fraction may be mixed with the C3 fraction.

  In the biomass treatment by fluid catalytic cracking in the present invention, an oxygen-containing compound derived from an ester in the biomass enters the product distillation column described above, thereby coking or fouling the bottom portion of the distillation column or its peripheral portion. Becomes intense. In order to prevent this, it is preferable that the bottom temperature of the distillation column included in the product recovery zone is 380 ° C. or lower. This temperature is more preferably 370 ° C. or lower, and further preferably 365 ° C. or lower. Coking here means that the heavy components in the liquid are solidified by polycondensation or the like, and if this adheres to valves, heat exchangers, pumps, etc., the liquid flow path is clogged and the heat transfer efficiency is reduced. Cause failure. In addition, such solid matter adhering / depositing on equipment or the like is sometimes called fouling.

  In the present invention, the bottom part of the distillation column in fluid catalytic cracking is constituted by extracting the bottom oil from the bottom, lowering the temperature through a pump and a heat exchanger, and returning part of the oil to the distillation tower. It is preferable to use it for temperature control at the bottom of the tower and to extract a part from the system to obtain a product.

  In the fluid catalytic cracking in the present invention, the linear velocity of the extracted oil at the bottom of the tower flowing through the heat exchanger for controlling the bottom temperature of the distillation tower included in the product recovery zone is 0.2 m / s or more. It is preferable that it is 0.5 m / s or more.

  In the fluid catalytic cracking according to the present invention, the residence time of the liquid at the bottom of the distillation column included in the product recovery zone is preferably 400 seconds or less. More preferably, the residence time is 300 seconds or less. The residence time here refers to a numerical value obtained by calculating the amount of liquid remaining in the tower bottom from the liquid level in the steady state of the tower bottom and dividing this by the flow rate of the tower bottom liquid.

  Furthermore, in the fluid catalytic cracking in the present invention, the bottom oil extracted from the bottom of the distillation column contained in the product recovery zone can be applied to a filter or a strainer. As a result, the caulking substance and the fouling substance can be removed from the bottom liquid and the operation can be continued more stably.

  In the fluid catalytic cracking in the present invention, water aggregation occurs because the temperature at the top of the first distillation column and in the vicinity thereof are below the dew point of water. The ester part contained in the biomass is mainly converted to water by the FCC treatment, and a part of the ester remains as an acid. By this combination of water and acid, the top of the first distillation column and its vicinity Corrosion becomes severe with equipment. In order to prevent this, it is preferable to process under the following conditions. By adopting this condition, it is possible to limit the amount of water and acid replicated from the biomass, and processing by conventional FCC becomes possible.

X <mw / 18
X: Ratio of fats and oils derived from biomass to all raw material oils (mass%)
mw: Molecular weight of biomass oil

  In the fluid catalytic cracking in the present invention, the coke yield is increased by the biomass treatment. As described above, since it is necessary to maintain the heat balance in FCC, in order to maintain the coke yield within an allowable range, the mixing ratio of the fats and oils derived from biomass in the FCC feedstock oil should be within the range of the following formula. preferable. Under this condition, the heat balance can be maintained. Furthermore, if the following equation is used, it is possible to prevent the emission amount of carbon dioxide from increasing.

X <C (RR ′) / 1.4
X: Ratio of fats and oils derived from biomass in the raw oil of the fluid catalytic cracker (mass%)
R: In the fluid catalytic cracking device, only the mineral oil not mixed with biomass is operated.
Ratio of residual oil in mineral oil raw material
R ′: an operation for processing a raw material mixed with biomass in the fluid catalytic cracking apparatus.
Ratio of mineral oil-based residual oil in all raw materials when performing (mass%)
C: Residual coal concentration (mass%) in the residual oil

The gasoline of the present invention comprises all or part of a fraction having a distillation temperature range of 25 ° C. to 220 ° C. obtained by treating biomass or a raw oil mixed with biomass and mineral oil by fluid catalytic cracking. Contains a substrate.
Examples of the fraction range include a light fraction of 25 ° C to 70 ° C, an intermediate 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 25 ° C. to 220 ° C. fraction can be used as the base material.
From the viewpoint of octane number, a light fraction is preferable, specifically, a fraction of 150 ° C. or lower is preferable, a fraction of 120 ° C. or lower is more preferable, and a fraction of 100 ° C. or lower is more preferable.

  In the gasoline of the present invention, when blending a base material obtained by treating the raw material oil mixed with biomass or biomass and mineral oil by fluid catalytic cracking, if necessary, desulfurization is performed on this base material. Can be processed. The treatment such as desulfurization may be performed for the entire fraction of the base material to be blended or a part of the fraction. Examples of desulfurization methods include selective hydrodesulfurization processes that suppress the hydrogenation reaction of olefins in the substrate as much as possible, non-selective hydrodesulfurization processes that provide high desulfurization rates, adsorptive desulfurization processes, membrane separation processes, etc. Is mentioned. In addition, when the octane number of a base material falls by these desulfurization processes, the process etc. which further recover an octane number can also be combined.

  The gasoline of the present invention comprises all or part of a fraction having a distillation temperature range of 25 ° C. to 220 ° C. obtained by treating biomass or a raw oil mixed with biomass and mineral oil by fluid catalytic cracking. Contains a substrate. The content of the base material is preferably 5% by volume or more, more preferably 10% by volume or more, and still more preferably 15% by volume from the viewpoint of containing a large amount of biomass-derived base material. On the other hand, in order to adjust the properties of the gasoline of the present invention to a more preferable range, the content of the biomass-derived base material is preferably 75% by volume or less, more preferably 50% by volume or less, More preferably, it is not more than volume%.

The gasoline of the present invention comprises all or part of a fraction having a distillation temperature range of 25 ° C. to 220 ° C. obtained by treating biomass or a raw oil mixed with biomass and mineral oil by fluid catalytic cracking. Except for the base material, the base material to be blended is not particularly limited, and one or two or more gasoline base materials that can be produced by any conventionally known method can be blended.
Specifically, light naphtha obtained by atmospheric distillation of crude oil, heavy naphtha, desulfurized heavy naphtha obtained by desulfurizing heavy naphtha, hydrocracked gasoline obtained by hydrocracking, catalytic reforming Reformed gasoline obtained by the quality method (hole range reformed gasoline (boiling range: 30 to 200 ° C) divided by boiling range), light reformed gasoline (boiling range: 20 to 100 ° C), medium reformed gasoline (boiling point) (Range: 60-180 ° C), heavy reformed gasoline (boiling point range: 140-275 ° C), including a mixture of two or more of each reformed gasoline), the residue from which aromatics were extracted from the reformed gasoline Some raffinates, polymerized gasoline obtained by polymerizing olefins, alkylates obtained by adding (alkylating) lower olefins to hydrocarbons such as isobutane, and isomerizing light naphtha The isomerized gasoline, denormalized paraffin oil, butane, aromatic hydrocarbon compound, and propylene obtained by conversion to isoparaffin in the reactor are dimerized, followed by hydrogenation of the paraffin fraction and natural gas. Examples include GTL (Gas to Liquids) light fractions obtained by FT (Fischer-Tropsch) synthesis after decomposition into carbon oxide and hydrogen. Separately from the base material obtained by treating the raw material oil mixed with biomass or biomass and mineral oil, which is an essential base material of the present invention, by fluid catalytic cracking, catalytic cracking gasoline using only mineral oil as the raw material oil Can also be blended separately.

The blending amounts of these base materials are arbitrary as long as the gasoline of the present invention is adjusted so as to have a necessary property range, but typical examples of the blending ranges of base materials are shown below.
(1) Reformed gasoline: 0 to 80% by volume
(2) Alkylate: 0 to 40% by volume
(3) Isomerized gasoline: 0-30% by volume
(4) Light naphtha: 0 to 10% by volume
(5) Destilled heavy naphtha: 0 to 20% by volume
(6) Butane: 0 to 10% by volume

The gasoline research octane number (RON) of the present invention needs to be 96.0 or more in order to prevent knocking, improve drivability, and maximize the performance of a premium gasoline specification vehicle. Preferably it is 98.0 or more, More preferably, it is 99.5 or more, Most preferably, it is 100.0 or more. Further, 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 is preferably 85.0 or more, and more preferably 87.0 or more.
The research method octane number (RON) and the motor method octane number (MON) as used herein mean the research method octane number and the motor method octane number measured by JIS K 2280 “Testing method for octane number and cetane number”.

The sulfur content of the gasoline of the present invention needs to be 10 mass ppm or less, preferably 8 mass ppm or less, more preferably 5 mass ppm or less. If the sulfur content exceeds 10 ppm by mass, the performance of the exhaust gas purification catalyst may be adversely affected, the concentration of NOx, CO, and HC in the exhaust gas may increase, and the amount of benzene emitted may increase. This is not preferable.
The sulfur content here means a value measured according to JIS K 2541 “Crude oil and petroleum products—Sulfur content test method”.

  The gasoline of the present invention needs to be unleaded. The term “lead-free” as used herein means that an alkyl lead compound such as tetraethyl lead is not substantially added. Even when a very small amount of lead compound is contained, the content is JIS K 2255 “in gasoline. It means that it is not more than the application category lower limit value (0.001 g / l) of “lead content test method”.

The distillation initial boiling point (IBP) of the gasoline of the present invention is preferably 20 ° C. or higher, more preferably 23 ° C. or higher. When IBP 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. When IBP exceeds 37 ° C., low temperature drivability may be reduced.
The 10% distillation temperature (T10) of the gasoline of the present invention is preferably 35 ° C. or higher, more preferably 40 ° C. or higher. When T10 is less than 35 ° C., hydrocarbons in the exhaust gas may increase, and high temperature operability may decrease due to vapor lock. On the other hand, T10 is preferably 70 ° C. or lower, more preferably 60 ° C. or lower. When T10 exceeds 70 ° C, the low temperature startability may be reduced.
The 30% distillation temperature (T30) of the gasoline of the present invention is preferably 55 ° C or higher, more preferably 60 ° C or higher. If T30 is less than 55 ° C., fuel consumption may be deteriorated. On the other hand, T30 is preferably 77 ° C or lower, more preferably 75 ° C or lower, and further preferably 70 ° C or lower. When T30 exceeds 77 ° C, the medium / low temperature drivability may be lowered.

The 50% distillation temperature (T50) of the gasoline of the present invention is preferably 75 ° C. or higher, more preferably 80 ° C. or higher, from the viewpoint of preventing deterioration of fuel consumption. On the other hand, from the viewpoint of preventing deterioration in normal temperature drivability, T50 is preferably 110 ° C. or lower, more preferably 105 ° C. or lower, and further preferably 100 ° C. or lower.
The 70% distillation temperature (T70) of the gasoline of the present invention is preferably 95 ° C. or higher. When T70 is less than 95 ° C., fuel consumption may be deteriorated. On the other hand, T70 is preferably 135 ° C. or lower, more preferably 130 ° C. or lower. When T70 exceeds 135 ° C., the medium / low temperature operability during cold operation may decrease, and there may be an increase in hydrocarbons in exhaust gas, an increase in intake valve deposits, and an increase in combustion chamber deposits. .
The 90% distillation temperature (T90) of the gasoline of the present invention is preferably 115 ° C or higher, more preferably 120 ° C or higher. When T90 is less than 115 ° C., fuel consumption may be deteriorated. On the other hand, T90 is preferable from the viewpoint of preventing deterioration of low temperature and normal temperature drivability during cold operation, increase in dilution of engine oil with gasoline, increase in hydrocarbon exhaust gas, deterioration of engine oil and generation of sludge. Is 180 ° C. or lower, more preferably 170 ° C. or lower, and still more preferably 165 ° C. or lower.
The distillation end point (EP) of the gasoline of the present invention is preferably 150 ° C. or higher. Further, EP is preferably 220 ° C. or lower, more preferably 200 ° C. or lower, and further preferably 195 ° C. or lower. If EP exceeds 220 ° C., intake valve deposits and combustion chamber deposits may increase, and spark plug smoldering may occur.
Here, IBP, T10, T30, T50, T70, T90, and EP mean values (° C.) measured by JIS K 2254 “Petroleum products—distillation test method”.

The lead vapor pressure (RVP) of the gasoline of the present invention is preferably adjusted according to the season and region in which the gasoline is used. Specifically, for warm seasons and regions, 44 to 72 kPa is preferable, 44 to 65 kPa is more preferable, 50 to 65 kPa is further preferable, and 55 to 65 kPa is most preferable. 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 further preferable, and 70 to 88 kPa is most preferable. If the RVP is high, there may be a problem in drivability due to vapor lock or the like, and if the RVP is low, the startability in the cold state may be deteriorated.
The vapor pressure (RVP) here refers to a value (kPa) measured by JIS K 2258 “Crude oil and fuel oil vapor pressure test method (Lead method)”.

Density at 15 ℃ gasoline of the present invention, from the viewpoint of suppressing deterioration of the fuel economy, preferably 0.710 g / cm ³ or more, more preferably 0.720 g / cm ³ or more, 0.730 g / cm ³ or more and more Preferably, 0.735 g / cm ³ or more is most preferable. On the other hand, density at 15 ℃, from the viewpoint of preventing the smoldering acceleration of deterioration or plug, preferably 0.783g / cm ³ or less, more preferably 0.770 g / cm ³ or less, 0.760 g / cm ³ or less Is more preferable.
Here, the density at 15 ° C. means a value (g / cm ³ ) measured according to JIS K 2249 “Density test method and density / mass / capacity conversion table for crude oil and petroleum products”.

The oxidation stability of the gasoline of the present invention is preferably 240 minutes or more, more preferably 480 minutes or more, and further preferably 1440 minutes or more, from the viewpoint of suppressing the formation of gum during storage. .
The oxidation stability here means a value (minutes) measured by JIS K 2287 “Gasoline oxidation stability test method (induction period method)”.

The gasoline of the present invention preferably has a copper plate corrosion (50 ° C., 3 h) of 1 or less, more preferably 1a. If the copper plate corrosion exceeds 1, the fuel system conduit may corrode.
The copper plate corrosion here means a value measured according to JIS K 2513 “Petroleum products—copper plate corrosion test method” (test temperature 50 ° C., test time 3 hours).

The actual washing amount of the gasoline of the present invention is preferably 5 mg / 100 ml or less, more preferably 3 mg / 100 ml or less, and even more preferably 1 mg / 100 ml or less. Moreover, it is preferable that the amount of unwashed actual gum of the gasoline of the present invention is 20 mg / 100 ml or less. When the unwashed actual gum amount and the washed actual gum amount exceed the above values, there is a concern that precipitates are generated in the fuel introduction system or the suction valve is stuck.
As used herein, the amount of washed actual gum and the amount of unwashed actual gum mean values (mg / 100 ml) measured according to JIS K 2261 “Petroleum products—automobile gasoline and aviation fuel oil—existing gum test method—injection evaporation method”. To do.

The benzene content in the gasoline of the present invention is preferably 1% by volume or less. 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 (volume%) measured according to JIS K 2536 “Petroleum products—component test method—aromatic test method by gas chromatography”.

The aromatic content in the gasoline of the present invention is preferably 45% by volume or less, and more preferably 42% by volume or less. If the aromatic content exceeds 45% by volume, intake valve deposits and combustion chamber deposits may increase, and spark plug smoldering may occur. In addition, the concentration of benzene in the exhaust gas may increase. On the other hand, the aromatic content is preferably 20% by volume or more, and more preferably 25% by volume or more. If the aromatic content is less than 20% by volume, the fuel efficiency may deteriorate.
The aromatic content here means the aromatic content (volume%) in gasoline measured by JIS K 2536 “Petroleum products—component test method—fluorescent indicator adsorption method”.

The olefin content in the gasoline of the present invention is preferably 35% by volume or less, and more preferably 25% by volume or less. When the olefin content exceeds 35% by volume, there is a possibility that the oxidation stability of gasoline is deteriorated and the intake valve deposit is increased.
The olefin content here means the olefin content (volume%) in gasoline measured by JIS K 2536 “Petroleum products—component test method—fluorescent indicator adsorption method”.

The gasoline of the present invention may contain an oxygen-containing compound.
Examples of the oxygen-containing compound include alcohols having 2 to 4 carbon atoms and ethers having 4 to 8 carbon atoms. Specific examples of oxygen-containing compounds include ethanol, methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), tert-amyl methyl ether (TAME), and tert-amyl ethyl ether. it can. Of these, ethanol, MTBE, and ETBE are preferable. From the viewpoint of suppressing carbon dioxide emission, ethanol derived from biomass and ETBE produced using biomass-derived ethanol as a raw material can be particularly preferably used. Methanol is not detected when tested in accordance with JIS K 2536 “Petroleum product-component test method” (0.5% by volume) because it is corrosive and may increase the concentration of aldehyde in the exhaust gas. It is preferable that
The oxygen-containing compound content in the gasoline of the present invention is preferably 3.8% by mass or less in terms of oxygen atom from the viewpoint of compatibility with automobile fuel system members and suppression of increase in NOx in exhaust gas. 3.5 mass% or less, more preferably 2.7 mass% or less, and most preferably 1.3 mass% or less.

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, the startability of the engine may deteriorate.
Here, the amount of kerosene mixed is determined by the content of normal paraffin hydrocarbons having 13 and 14 carbon atoms on the basis of the total amount of gasoline, and the converted value of kerosene obtained according to the provisions of JIS K 2536 “Petroleum products-component test method” Is 4% by volume or less.

2 mass ppm or less is preferable and, as for content of manganese in the gasoline of this invention, 1 mass ppm or less is more preferable. The content of iron in the gasoline of the present invention is preferably 2 ppm by mass or less, and more preferably 1 ppm by mass or less. The content of sodium in the gasoline of the present invention is preferably 2 ppm by mass or less, and more preferably 1 ppm by mass or less. The potassium content in the gasoline of the present invention is preferably 2 ppm by mass or less, and more preferably 1 ppm by mass or less. The phosphorus content in the gasoline of the present invention is preferably 2 ppm by mass or less, more preferably 1 ppm by mass or less, and even more preferably 0.2 ppm by mass or less. If the contents of manganese, iron, sodium, potassium, and phosphorus exceed the above values, the efficiency of the exhaust gas purification system will increase 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, etc. May decrease.
The manganese, iron, and sodium contents here 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 Test Method”. for Phosphorus in Gasoline ”.

The gasoline of the present invention preferably contains an antioxidant and a metal deactivator for storage stability. Specifically, examples of the antioxidant include phenylenediamines such as N, N′-diisopropyl-p-phenylenediamine and N, N′-diisobutyl-p-phenylenediamine, and 2,6-di-t-butyl. Known compounds can be used as alkylphenol-based antioxidants such as hindered phenols represented by -4-methylphenol, and N, N'-disalicylidene-1,2 is used as a metal deactivator. -Known compounds can be used as metal deactivators such as amine carbonyl condensation compounds such as diaminopropane.
There are no particular restrictions on the amount of antioxidant or metal deactivator added, but the aforementioned oxidation stability is a preferred value, and the amount of unwashed real gum in the gasoline composition after addition including other additives is It is preferable to set the above-mentioned preferable value. Specifically, the antioxidant is preferably 5 to 100 mg / l, more preferably 10 to 50 mg / l. Moreover, 0.5-10 mg / l is preferable and, as for a metal deactivator, 1-5 mg / l is more preferable.

The gasoline of the present invention preferably contains a cleaning dispersant in order to prevent deposits such as intake valves from depositing. As the cleaning dispersant, compounds known as gasoline cleaning dispersants such as succinimide, polyalkylamine, and polyetheramine can be used. Among these, those having no residue when pyrolysis is performed at 300 ° C. in air are desirable. More preferably, polyisobutenylamine and / or polyetheramine is used.
The content of the cleaning dispersant is preferably 25 to 1000 mg per liter of gasoline of the present invention, more preferably 50 to 500 mg from the viewpoint of preventing intake valve deposits and further reducing combustion chamber deposits, ˜300 mg is most preferred. In the cleaning dispersant, an active ingredient that contributes to cleanliness may be diluted with an appropriate solvent. In such a case, the above-mentioned addition amount means an addition amount as an active ingredient.

  The gasoline of the present invention preferably contains a friction modifier in order to improve lubricity. Examples of the main friction modifier include, for example, alcohol; alcohol compound having 1 to 30 carbon atoms having 1 to 4 hydroxyl groups; carboxylic acid; hydroxyl group which is a reaction product of monocarboxylic acid and glycol or trihydric alcohol Containing ester; ester of polycarboxylic acid and polyhydric alcohol; and> NR (R is a hydrocarbon group having 5 to 40 carbon atoms), showing at least one nitrogen having one or more substituents Examples include esters of polyhydric alcohols in combination with compounds; amide compounds of carboxylic acids and alcohol amines, and the like. These can be used alone or as a mixture. Among these, a hydroxyl group-containing ester which is a reaction product of a monocarboxylic acid having 10 to 25 carbon atoms and glycol or a trihydric alcohol and / or an amide compound of a carboxylic acid having 5 to 25 carbon atoms and an alcohol amine are included. More preferably, an amide compound of a monocarboxylic acid having 10 to 25 carbon atoms and glycerin ester and / or a monocarboxylic acid having 5 to 25 carbon atoms and diethanolamine is more preferable.

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 viewpoint 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, more preferably 30 per liter of gasoline of the present invention. It is good to add so that it may become a content rate of -250 mg.
In addition, since a product marketed as a friction modifier is sometimes diluted with an appropriate solvent for an active ingredient that contributes to wear resistance, such a commercial product is added to the gasoline of the present invention. Means the addition amount as an active ingredient.

Other fuel oil additives that can be added to the gasoline of the present invention include surface ignition preventives such as organophosphorus compounds, anti-icing agents such as polyhydric alcohols or ethers thereof, alkali metal salts or alkalis of organic acids. Auxiliary agents such as earth metal salts, higher alcohol sulfates, anionic surfactants, cationic surfactants, antistatic agents such as amphoteric surfactants, colorants such as azo dyes, organic carboxylic acids or their derivatives Rust inhibitors such as alkenyl succinic acid esters, draining agents such as sorbitan esters, discriminating agents such as kilyzanine and coumarin, and odorants such as natural essential oil synthetic fragrances.
One or two 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.

  The present invention makes it possible to use biomass such as animal and vegetable fats and oils as gasoline, and to draw out excellent exhaust gas purification performance, fuel efficiency performance, and driving performance of gasoline automobiles.

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

[Examples 1 and 2 and Comparative Examples 1 and 2]
Using a fluid catalytic cracking apparatus having a regeneration zone, a reaction zone, a separation zone, a stripping zone and a product recovery zone, a raw material oil in which 30% by mass of soybean oil (average molecular weight 880) and 70% by mass of mineral oil are mixed. The reaction zone outlet temperature is 500 ° C., the catalyst / oil mass ratio is 6, the reaction pressure is 1.5 kg / cm ² G (147 kPa gauge pressure), the contact time between the raw material oil and the catalyst is 1.5 seconds, and the super stable Y type The base material A was obtained by processing with a catalyst containing 30% by mass of zeolite. The bottom temperature of the distillation column included in the product recovery zone at this time was adjusted to 340 ° C.
A flow having 30% by mass of vegetable oil (average molecular weight 850) mixed with palm oil and rapeseed oil and 70% by mass of mineral oil and having a regeneration zone, reaction zone, separation zone, stripping zone and product recovery zone Using a catalytic cracker, the reaction zone outlet temperature is 500 ° C., the catalyst / oil mass ratio is 6, the reaction pressure is 1.5 kg / cm ² G (147 kPa gauge pressure), and the contact time between the feedstock and the catalyst is 1.5. The substrate B was obtained by treating with a catalyst containing 30% by mass of ultrastable Y-type zeolite for 2 seconds. The bottom temperature of the distillation column included in the product recovery zone at this time was adjusted to 340 ° C.
Table 2 shows the ratios of base materials such as base material A, base material B, and catalytic cracked gasoline (raw material that does not contain biomass), alkylate, reformed gasoline, straight-run light naphtha, toluene, normal butane, etc. The test gasolines of Examples 1 and 2 and Comparative Examples 1 and 2 were prepared. Table 1 shows the properties of the base material used, and Table 3 shows the properties of the prepared test gasoline.

(Property measurement)
The properties of the substrate and the properties of the test gasoline in the examples and comparative examples were measured by the following methods.
The research method octane number and the motor method octane number are values based on the research method octane number and the motor method octane number measured according to JIS K 2280 “Testing method for octane number and cetane number”.
The sulfur content was measured according to JIS K 2541 “Crude oil and petroleum products—sulfur content test method”.
The lead content was measured according to JIS K 2255 “Test method for lead content in gasoline”.
The distillation properties (IBP, T10, T30, T50, T70, T90, EP) were all measured according to JIS K 2254 “Petroleum products—Distillation test method—Atmospheric pressure method”.
The vapor pressure (@ 37.8 ° C.) was measured according to JIS K 2258 “Crude oil and fuel oil vapor pressure test method (Lead method)”.
The density (@ 15 ° C.) was measured according to JIS K 2249 “Crude oil and petroleum product density test method and density / mass / capacity conversion table”.
The oxidation stability was measured according to JIS K 2287 “Gasoline Oxidation Stability Test Method (Induction Period Method)”.
Copper plate corrosion was measured in accordance with JIS K 2513 “Petroleum products—Copper plate corrosion test method” (test temperature 50 ° C., test time 3 hours).
The unwashed actual gum amount and the washed actual gum amount were measured according to JIS K 2261 “Petroleum products—Automotive gasoline and aviation fuel oil—Real gum test method—Jet evaporation method”.
Benzene was measured according to JIS K 2536 “Petroleum products—component test method—aromatic test method using gas chromatography”.
The aromatic content and olefin content were measured according to JIS K 2536 “Petroleum products—component test method—fluorescent indicator adsorption method”.
The kerosene content was measured in accordance with the provisions of JIS K 2536 “Petroleum product-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 ASTM D3231 “Standard Test Method for Phosphorus in Measured by “Gasoline”.

(Amount of carbon derived from biomass)
About the gasoline of an Example and a comparative example, the carbon amount derived from biomass was calculated | required by calculation from the throughput of a biomass, the compounding quantity of a base material, a density, carbon content, etc.

(Acceleration performance evaluation)
The 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 the test vehicle is sufficiently warmed up, the full acceleration from 50 km / h to 110 km / h is performed 10 times in the D range (OD is on), and it is necessary to reach 60 km to 100 km / h. The time was measured, and the average value of the seven required times excluding the first three times was defined as the acceleration time.

[Test vehicle]
Engine: Inline 4 cylinder (Premium gasoline specification, with supercharger)
Displacement: 1998cc
Injection system: Multi-point system Mission: Automatic transmission Exhaust gas purification system: Three-way catalyst, air-fuel ratio feedback control Complies with 2000 exhaust gas regulations

(Exhaust gas test)
In the exhaust gas test, the emissions of CO and NOx contained in the exhaust gas were measured using the above-described test vehicle in accordance with the technical guidelines of the gasoline automobile 10.15 mode exhaust gas measurement by the Ministry of Land, Infrastructure, Transport and Tourism.

(Fuel consumption test)
The fuel consumption test was measured using the above-described test vehicle according to the gasoline automobile 10.15 mode fuel consumption test method by the Ministry of Land, Infrastructure, Transport and Tourism.

  As shown in Table 4, the gasoline of the present invention (Examples 1 and 2) contains biomass-derived carbon, and can realize good acceleration performance, low exhaust gas (CO, NOx) level, and good fuel efficiency. I understand.

Claims (11)

  It contains a base material consisting of all or part of a fraction whose distillation temperature range is 25 ° C to 220 ° C obtained by treating biomass or raw material oil mixed with biomass and mineral oil by fluid catalytic cracking. A gasoline with a research octane number of 96.0 or more and a sulfur content of 10 mass ppm or less. The treatment by fluid catalytic cracking uses a fluid contact device having a regeneration zone, a reaction zone, a separation zone, a stripping zone and a product recovery zone. The reaction zone outlet temperature is 480 to 540 ° C., and the catalyst / oil mass ratio is 4. To 12, a reaction pressure of 1 to 3 kg / cm ² G (98 to 294 kPa gauge pressure), a contact time of the raw material oil and the catalyst of 1 to 3 seconds, and a catalyst containing 10 to 50% by mass of ultrastable Y-type zeolite is used. The gasoline according to claim 1, which is performed under conditions.   The gasoline according to claim 1 or 2, wherein the bottom temperature of the distillation column included in the product recovery zone of the fluid catalytic cracking apparatus is 380 ° C or lower. The gasoline according to any one of claims 1 to 3, wherein the ratio (mass%) of the fat and oil derived from biomass to the total raw material oil in fluid catalytic cracking is represented by the following formula.
X <mw / 18
X: Ratio of fats and oils derived from biomass to all raw material oils (mass%)
mw: Molecular weight of biomass oil   The content of the base material consisting of all or a part of a fraction whose distillation temperature range is 25 ° C to 220 ° C obtained by processing biomass or raw material oil mixed with biomass and mineral oil by fluid catalytic cracking The gasoline according to any one of claims 1 to 4, which is 5% by volume or more and 75% by volume or less based on the total amount of gasoline. 10% distillation temperature is 70 ° C. or less, 50% distillation temperature is 75 ° C. or more and 110 ° C. or less, 90% distillation temperature is 180 ° C. or less, distillation end point is 220 ° C. or less, and vapor pressure (37.8 ° C.) is 44 kPa. 93 kPa or less, density (15 ° C.) is 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 / 100 ml or less, unwashed The gasoline according to any one of claims 1 to 5, wherein the real gum is 20 mg / 100 ml or less and the benzene content is 1 vol% or less.   The gasoline according to any one of claims 1 to 6, wherein the aromatic content is 45 vol% or less and the olefin content is 35 vol% or less.   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 is 2 mass ppm or less. The gasoline according to any one of claims 1 to 7, wherein   The gasoline according to any one of claims 1 to 8, comprising an antioxidant and a metal deactivator.   The gasoline according to any one of claims 1 to 9, further comprising a cleaning dispersant.   The gasoline according to any one of claims 1 to 10, further comprising a friction modifier.