JP6196938B2 - Gasoline composition - Google Patents

Description

  The present invention relates to a gasoline composition.

Among gasoline fractions obtained from highly aromatic hydrocarbon oils such as cracked light diesel oil (LCO), for example, aromatic compounds having 8 carbon atoms have been used as petrochemical raw materials. However, in recent years, demand for petrochemical raw materials has also increased for aromatic compounds having 9 carbon atoms.
Therefore, there is a demand for a gasoline composition that is inferior in performance even without using a high-value-added gasoline fraction that can be used as a petrochemical raw material, and that has even better performance than before.
As an example of a technology that improves gasoline performance by combining gasoline base materials, light cracked gasoline or alkylate gasoline obtained by distilling low-boiling and high-octane catalytic cracked gasoline into 50% A technique for increasing the octane number of a gasoline composition by adjusting the outlet temperature and the 90% distillation temperature low has been proposed (see Patent Document 1).
On the other hand, as a gasoline composition, further improvement in low-temperature drivability in winter has been desired.

JP-A-2005-290159

  An object of the present invention is to provide a gasoline composition that is excellent in operability even in winter and generates less combustion chamber deposits while reducing the content of aromatic compounds having 8 and 9 carbon atoms in the base material. .

The present inventors have found that a gasoline composition having excellent characteristics can be obtained by selecting a base material such that the lead vapor pressure and the 90% distillation temperature are in a specific range. That is, the present invention provides the following gasoline composition.
[1] Reed vapor pressure is 68 kPa or more and 93 kPa or less, 50% distillation temperature is 75 ° C. or more and 105 ° C. or less, 90% distillation temperature is 100 ° C. or more and 150 ° C. or less, and aromatic compound Composition containing 20 volume% or more and 45 volume% or less with respect to the total volume of the composition, sulfur containing 10 mass ppm or less with respect to the total weight of the composition, and a research octane number of 96 or more and 103 or less .
[2] The gasoline composition according to [1], wherein the 70 ° C. distillation amount is 26% by volume or more.
[3] The gasoline composition according to [1] or [2], wherein the aromatic compound having 7 carbon atoms is contained in an amount of 20% by volume or more based on the total volume of the composition.
[4] The volume ratio (the aromatic compound having 9 carbon atoms / the aromatic compound having 7 carbon atoms) of the content of the aromatic compound having 9 carbon atoms and the content of the aromatic compound having 7 carbon atoms is 0 or more, 0 The gasoline composition according to any one of [1] to [3], which is 15 or less.
[5] The gasoline composition according to [1], wherein the total content of the aromatic compound having 8 carbon atoms and the content of the aromatic compound having 9 carbon atoms is 10% by volume or less with respect to the total capacity of the composition. .

  According to the present invention, the content of the aromatic compound having 8 carbon atoms and the content of the aromatic compound having 9 carbon atoms in the base material are reduced, and the operability is excellent even in winter, and the generation of the combustion chamber deposit is small. A gasoline composition can be provided.

[Gasoline composition]
The gasoline composition according to the embodiment of the present invention has a reed vapor pressure of 68 kPa or more and 93 kPa or less, a 50% distillation temperature of 75 ° C. or more and 105 ° C. or less, a 90% distillation temperature of 100 ° C. or more, 150 ° C. or less, aromatic compound is contained in an amount of 20% by volume or more and 45% by volume or less with respect to the total volume of the composition, sulfur is contained in 10% by mass or less with respect to the total mass of the composition, and the research octane number is 96 Above, it is below 103.

<Properties of gasoline composition>
The lead vapor pressure of the gasoline composition according to the embodiment of the present invention is 68 kPa or more and 93 kPa or less. If the reed vapor pressure is less than 68 kPa, engine startability at low temperatures tends to deteriorate. From this viewpoint, the reed vapor pressure is preferably 70 kPa or more, more preferably 72 kPa or more, and particularly preferably 76 kPa or more.
Further, if the reed vapor pressure exceeds 93 kPa, the amount (emission) of exhaust gas discharged from the vehicle during refueling or traveling increases. In addition, vapor lock is likely to occur in the fuel supply line, and engine restartability and running performance immediately after running at high temperatures are likely to deteriorate. From these viewpoints, the reed vapor pressure is preferably 91 kPa or less, more preferably 90 kPa or less, and particularly preferably 88 kPa or less.
Here, the lead vapor pressure is a vapor pressure at 37.8 ° C. measured by JIS K 2258 “Crude oil and fuel oil—Vapor pressure test method—Reed method”.

The 50% distillation temperature of the gasoline composition according to this embodiment is 75 ° C. or higher and 105 ° C. or lower. If the 50% distillation temperature is less than 75 ° C., the engine restartability and running performance immediately after running at high temperatures tend to deteriorate. In this respect, the 50% distillation temperature is preferably 76 ° C. or higher, more preferably 78 ° C. or higher, and particularly preferably 80 ° C. or higher.
On the other hand, if the 50% distillation temperature exceeds 105 ° C., the startability and running performance at low temperatures tend to deteriorate. From this viewpoint, the 50% distillation temperature is preferably 103 ° C. or lower, more preferably 100 ° C. or lower.

The 70% distillation temperature of the gasoline composition according to this embodiment is preferably 95 ° C or higher and 135 ° C or lower. When the 70% distillation temperature is 95 ° C. or higher, engine restartability and running performance immediately after running at high temperatures may be easily improved. In this respect, the 70% distillation temperature is more preferably 98 ° C. or higher, still more preferably 100 ° C. or higher, and particularly preferably 105 ° C. or higher.
Further, when the 70% distillation temperature is 135 ° C. or lower, the startability and running performance at low temperatures may be good. In this respect, the 70% distillation temperature is more preferably 130 ° C. or less, and still more preferably 128 ° C. or less.
Moreover, it is preferable that the 70 degreeC distillate of the gasoline composition which concerns on this embodiment is 26 volume% or more. When the 70 ° C. distillate is 26% by volume or more, the operability at low temperatures may be good.
In this respect, the 70 ° C. distillate is more preferably 27% by volume or more, and still more preferably 28% by volume or more.

The 90% distillation temperature of the gasoline composition according to this embodiment is 100 ° C. or higher and 150 ° C. or lower. If the 90% distillation temperature is less than 100 ° C., fuel efficiency is deteriorated. In this respect, the 90% distillation temperature is preferably 102 ° C. or higher, more preferably 105 ° C. or higher.
Further, when the 90% distillation temperature exceeds 150 ° C., the production of combustion chamber deposits increases. From this viewpoint, the 90% distillation temperature is preferably 145 ° C. or lower, and more preferably 140 ° C. or lower.

In the gasoline composition according to this embodiment, the difference between the 90% distillation temperature and the 70% distillation temperature is preferably less than 20 ° C. If the difference between the 90% distillation temperature and the 70% distillation temperature is less than 20 ° C., the production of combustion chamber deposits may be reduced. From this viewpoint, the difference between the 90% distillation temperature and the 70% distillation temperature is more preferably 15 ° C. or less, and further preferably 10 ° C. or less.
The distillation temperature is a value measured according to JIS K 2254 “Petroleum product-distillation test method (normal pressure method)”.

The research method octane number (RON) of the gasoline composition according to the present embodiment is 96 or more and 103 or less. If the RON is less than 96, the fuel consumption deteriorates. From this viewpoint, RON is preferably 97 or more, more preferably 98 or more.
On the other hand, if RON exceeds 103, exhaust gas quality is deteriorated due to an increase in aromatic compounds. Moreover, the drivability at the start-up is deteriorated due to the heavy distillation properties. From this viewpoint, RON is preferably 102 or less, more preferably 101 or less.

Density at 15 ℃ gasoline composition according to the present embodiment is preferably 0.71 g / cm ³ or more and 0.77 g / cm ³ or less, more preferably 0.715 g / cm ³ or more, 0.765 g / cm ^{3 or} less, particularly preferably 0.73 g / cm ³ or more and 0.76 g / cm ³ or less. When the density at 15 ° C. is in the above range, the calorific value can be increased and the combustibility can be improved, so that the fuel consumption can be kept good.
In addition, the density in 15 degreeC is a density measured by JISK2249 "the density test method and density / mass / capacity conversion table of crude oil and petroleum products".

The gasoline composition according to the present embodiment contains 10 ppm by mass or less of sulfur with respect to the total mass of the composition. The sulfur content in the gasoline composition becomes sulfur oxide in the exhaust gas, and poisons the nitrogen oxide removal catalyst. Fuel is used to create a reducing atmosphere to restore the activity of the nitrogen oxide removal catalyst. For this reason, if the sulfur content in the gasoline composition exceeds 10 ppm by mass, the nitrogen oxide removal catalyst is easily poisoned, and the fuel consumption in the gasoline composition is deteriorated. From this viewpoint, the sulfur content in the gasoline composition is preferably 9 ppm by mass or less, more preferably 8 ppm by mass or less, and particularly preferably 5 ppm by mass or less.
The sulfur content is a value measured according to JIS K2541-6 “Crude oil and petroleum products—Sulfur content test method Part 6: Ultraviolet fluorescence method”.

<Base material component>
Examples of the base material constituting the gasoline composition according to the present embodiment include light cracked gasoline (LFG), alkylate gasoline (ALG), aromatic compounds having 7, 8, and 9 carbon atoms, and olefinic hydrocarbons. In addition, alkylate gasoline (ALG) is obtained by alkylating a butene fraction and an isobutane fraction.

The gasoline composition according to the present embodiment includes, in addition to the above-described base material, a reformed product that contains a C7, C8 and C9 aromatic compound obtained by further distillation of catalytically reformed gasoline. Gasoline fraction is included.
In the gasoline composition according to this embodiment, among the aromatic compounds having 7 carbon atoms, 8 carbon atoms, and 9 carbon atoms, the aromatic compound having 7 carbon atoms is 20% by volume or more based on the total volume of the gasoline composition. It is preferably included.
When the aromatic compound having 7 carbon atoms is contained in an amount of 20% by volume or more with respect to the total volume of the composition, the octane number can be increased. In this respect, the aromatic compound having 7 carbon atoms is more preferably 25% by volume or more, and further preferably 30% by volume or more.
Further, the volume ratio of the content of the aromatic compound having 9 carbon atoms and the content of the aromatic compound having 7 carbon atoms (aromatic compound having 9 carbon atoms / aromatic compound having 7 carbon atoms) is 0 or more; It is preferable that it is 15 or less.
When the volume ratio of the content of the aromatic compound having 7 carbon atoms and the content of the aromatic compound having 9 carbon atoms is the above ratio, there is an effect of reducing the deposit. From this viewpoint, the volume ratio of the content of the aromatic compound having 7 carbon atoms and the content of the aromatic compound having 9 carbon atoms is more preferably 0 or more and 0.14 or less, and still more preferably 0 or more. 0.10 or less.

Furthermore, in the gasoline composition according to the present embodiment, the total of the content of the aromatic compound having 8 carbon atoms and the content of the aromatic compound having 9 carbon atoms is 10% by volume or less with respect to the total volume of the composition. Preferably there is. The fact that the total of the content of aromatic compounds having 8 carbon atoms and the content of aromatic compounds having 9 carbon atoms can be reduced to the above range is different from the aromatic compounds having 8 carbon atoms and the aromatic compounds having 9 carbon atoms. The amount used for the above application can be increased, and the substrate can be used effectively.
In this respect, the total content of the aromatic compound having 8 carbon atoms and the content of the aromatic compound having 9 carbon atoms is more preferably 8% by volume or less with respect to the total volume of the composition, and 5 volume. % Or less is particularly preferable.

The gasoline composition according to the present embodiment may contain an olefinic hydrocarbon. Examples of the olefinic hydrocarbon include light catalytic cracking gasoline (LFG) and olefinic hydrocarbon having 5 carbon atoms. The olefinic hydrocarbon having 5 carbon atoms is obtained by separating cracked oil obtained when pyrolyzing naphtha to produce ethylene.
If the olefinic hydrocarbon is contained in an amount of 10% by volume or more based on the total volume of the gasoline composition, an effect of improving the research octane number (RON) can be obtained. In this respect, the olefinic hydrocarbon is more preferably 13% by volume or more, and still more preferably 16% by volume or more.
Further, when the olefinic hydrocarbon is contained in an amount of 30% by volume or less based on the total gasoline composition volume, the intake valve deposit is not increased without deteriorating the oxidation stability of the gasoline. In this respect, the olefinic hydrocarbon is more preferably 28% by volume or less, and still more preferably 25% by volume or less, based on the total volume of the gasoline composition.

  The gasoline composition according to the present embodiment may appropriately contain an oxygen-containing compound such as ethanol or ethyl t-butyl ether (ETBE) as a base other than the above.

In the gasoline composition according to this embodiment, the aromatic compound is contained in an amount of 20% by volume or more and 45% by volume or less based on the total volume of the gasoline composition. If the aromatic compound is less than 20% by volume, fuel consumption may be deteriorated due to a decrease in calorific value. In this respect, the aromatic compound is preferably 25% by volume or more, more preferably 30% by volume or more.
When the content of the aromatic compound exceeds 45% by volume with respect to the total volume of the gasoline composition, the exhaust gas properties are deteriorated and the plug is bent. In this respect, the aromatic compound is preferably contained in an amount of 43% by volume or less, and more preferably 42% by volume or less, based on the total volume of the gasoline composition.

<Additives>
In the gasoline composition according to the present embodiment, in addition to the above-described base material, the balance may include other petroleum-based fractions and additives such as fluidity improvers applicable to the gasoline composition. Good. Although the compounding quantity of an additive can be selected suitably, it is preferable to normally select the compounding quantity of this additive so that content of the additive in a gasoline composition can be maintained at 0.1 mass% or less.
Examples of additives that can be used in the gasoline composition according to the present embodiment include amine-based or phenol-based antioxidants, Schiff-type compounds, metal deactivators such as thioamide-type compounds, and organic phosphorus-based compounds. Anti-ignition agent, detergent / dispersant such as succinimide, polyalkylamine, polyetheramine, anti-icing agent such as polyhydric alcohol or its ether, alkali metal salt or alkaline earth metal salt of organic acid, sulfuric acid of higher alcohol Auxiliary agents such as esters, anionic surfactants, cationic surfactants, antistatic agents such as amphoteric surfactants, rust inhibitors such as alkenyl succinates, colorants such as azo dyes, fluidity improvers, etc. Can be mentioned.

[Method for producing gasoline composition]
The method for producing a gasoline composition according to the present embodiment is such that light cracked gasoline is 30% by volume or more, alkylate gasoline is 25% by volume or less, olefinic hydrocarbon is 10% by volume or more, based on the total volume of the gasoline composition. A step of preparing a gasoline composition so as to be contained by 30% by volume or less.
In addition, the manufacturing method of the gasoline composition which concerns on this embodiment is not limited to the above-mentioned method, as long as the property of the gasoline composition obtained satisfy | fills the said specified range.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. The properties of the test gasoline compositions prepared as examples and comparative examples were measured by the following methods.
・ Reed vapor pressure: JIS K 2258 "Crude oil and fuel oil-Vapor pressure test method-Reed method"
-Research octane number (RON): JIS K 2280 "Petroleum products-fuel oil-octane number and cetane number test method and cetane index calculation method"
Sulfur content: Value measured by JIS K 2541-6 “Crude oil and petroleum products—Sulfur content test method Part 6: Ultraviolet fluorescence method”.
Density (15 ° C.): Density measured according to JIS K 2249 “Crude oil and petroleum product density test method and density / mass / capacity conversion table”.
-Distillation property: It is a value measured by JIS K2254 "Petroleum products-Distillation test method".
・ Total aromatics, unsaturated, aromatics with 7 carbon atoms, aromatics with 8 carbons, aromatics with 9 carbons, and benzene are JIS K 2536 “Petroleum products-component test It was measured by the gas chromatography method in “Method”. The analysis conditions were as follows.

<Analysis conditions>
Column material: 100% methyl silicone capillary column Temperature conditions: initial temperature 5 ° C., holding time 10 minutes, heating rate 2 ° C./min, final temperature 140 ° C.
Gas conditions: flow rate 2 mL / min, split ratio 50: 1, makeup amount 50 mL / min,
Sample injection volume: 0.5 μL

Moreover, the gasoline composition was evaluated by the following method.
[Low temperature operation]
Using a chassis dynamo device, a operability test was conducted at a low temperature using a test car with a displacement of 660 cc and a fuel supply system of carburetor. The vehicle was kept cold and the drivability at low temperatures (−10 ° C.) was evaluated.
In the evaluation test, the room temperature was set to −10 ° C., and the test mode was set to the hesitation evaluation mode (2005 Petroleum Product Discussion Meeting: “Examination of the Effect of Gasoline Distillation Properties (T50) on Vehicle Drivability”). In accordance with the following procedures (i) and (ii).
(I) After cooling the vehicle so that the water temperature and the oil temperature become -10 ° C, the engine is idled for 10 seconds after the engine is started, accelerated at an accelerator opening of 50% and decelerated after the vehicle speed reaches 40 km / h. Stopped.
(Ii) Subsequently, acceleration and deceleration were repeated up to 20 times in total.
The low temperature performance was evaluated by demerit points. The demerit score is measured during the first to twentieth acceleration of the previous ice-freezing test, CRC (Coordinating Research Council) Report No. Evaluation was performed according to the evaluation method described in 483.
Specifically, when a malfunction in the driving performance shown in Table 1 occurs, the coefficient corresponding to the type of malfunction shown in Table 1 for each malfunction item and the degree of phenomenon shown in Table 2 The demerit score was calculated by multiplying the demerit score, and the demerit score of all items of the defect was totaled.
For stalls during idling and during running, such a multiplication is not performed, but a coefficient corresponding to the type of failure is simply added.

  The operability at low temperatures (−10 ° C.) is A if the demerit point is 30 or less, B if 30 to 40, C if 40 to 50, D (C and D are not good) if 50 or more. Passed)

[deposit]
The engine was operated in accordance with “JASO M 352 automobile gasoline engine, influence test method on intake chamber cleaner for combustion chamber deposit”, and the deposit adhered to the combustion chamber after operation was measured. The combustion chamber deposit (CCD) was measured as follows.
The deposit amount is the total of the deposits collected and weighed on the cylinder head and the piston top, and the average value of the four cylinders was used as the deposit amount.
When the deposit amount of each test gasoline composition was 400 mg / cylinder or less, it was A, when it was 400 to 600 mg / cylinder, B, and when it was 600 mg / cylinder or more, C (C was rejected).

[Examples and Comparative Examples]
Using the base materials shown in Table 3, blends were made according to the formulation of Table 4, and gasoline compositions of Examples and Comparative Examples were prepared. Further, as a detergent, 200 mass ppm of a polyisobuteneamine-based detergent (manufactured by BASF) was added.

The base materials used in the above table are as follows.
C7A (aromatic compound having 7 carbon atoms): a fraction mainly composed of 7 aromatic components in the aromatic components obtained by distillation separation from the reformed gasoline obtained by catalytic reforming of naphtha C9A (aromatic compound having 9 carbon atoms): a fraction mainly composed of aromatic components having 9 carbon atoms among aromatic components obtained by distillation separation from reformed gasoline obtained by catalytic modification of naphtha RAF (raffinate): Mainly saturated hydrocarbon obtained by distilling benzene and nearby saturated hydrocarbons from the reformed gasoline obtained by catalytic reforming of naphtha or desulfurized heavy naphtha and solvent extraction of benzene ALG (alkylated gasoline): hydrocarbon base material mainly composed of isoparaffin obtained by reacting a fraction mainly composed of butene and a fraction mainly composed of isobutane with a sulfuric acid catalyst LFG (light contact) Cracked gasoline): decompression A heavy gas oil fraction mainly composed of light oil or a residual oil obtained from atmospheric distillation equipment or vacuum desulfurization equipment is hydrodesulfurized, and then the heavy fraction of gasoline fraction obtained by fluid catalytic cracking is separated by distillation. A fraction having a 90% distillation temperature of 100 ° C. or lower ETBE: a commercial product having a purity of 97% by volume, and main impurities are 1.1% by volume of TBA (t-butyl alcohol) and 1% by volume of ethanol LPG (BS): Butane fraction

[Evaluation results]
The properties of the test gasoline composition were measured and evaluated. The results are shown in Table 4.

  From the results shown in Table 4, it is found that a gasoline composition having a Reed vapor pressure of 68 kPa to 93 kPa and a 90% distillation temperature of 100 ° C. to 150 ° C. is excellent in low temperature acceleration and depositability. It was.

Claims (7)

Reed vapor pressure is 68 kPa or more and 93 kPa or less, 50% distillation temperature is 75 ° C. or more and 105 ° C. or less, 90% distillation temperature is 100 ° C. or more and 140 ° C. or less, and an aromatic compound is a composition. 20 volume% or more relative to the total volume, contained 45 volume% or less, sulfur contained 10 ppm by mass or less relative to the total weight of the composition, research octane number is 96 or more, 103 I der below,
The aromatic compound having 7 carbon atoms is contained in an amount of 20% by volume or more based on the total volume of the composition,
The volume ratio of the content of the aromatic compound having 9 carbon atoms and the content of the aromatic compound having 7 carbon atoms (aromatic compound having 9 carbon atoms / aromatic compound having 7 carbon atoms) is 0 or more and 0.15 or less. And
A gasoline composition in which the sum of the content of aromatic compounds having 8 carbon atoms and the content of aromatic compounds having 9 carbon atoms is 10% by volume or less based on the total volume of the composition.   The gasoline composition according to claim 1, wherein the 70 ° C distillate is 26 vol% or more. The gasoline composition according to claim 1 or 2, wherein the aromatic compound having 7 carbon atoms is 25% by volume or more based on the total volume of the composition. The capacity ratio (the aromatic compound having 9 carbon atoms / the aromatic compound having 7 carbon atoms) of the content of the aromatic compound having 9 carbon atoms and the content of the aromatic compound having 7 carbon atoms is 0.14 or less. Item 4. The gasoline composition according to any one of Items 1 to 3. The sum of the content of the aromatic compound having 8 carbon atoms and the content of the aromatic compound having 9 carbon atoms is 8% by volume or less based on the total volume of the composition. Gasoline composition. The gasoline composition according to any one of claims 1 to 5, wherein the olefinic hydrocarbon is 30% by volume or less based on the total volume of the composition. The gasoline composition according to any one of claims 1 to 6, wherein the aromatic compound is 25% by volume or more based on the total volume of the composition.