JP4425606B2 - Unleaded high octane gasoline - Google Patents

Description

  The present invention relates to an unleaded high-octane gasoline, and more particularly to an unleaded high-octane gasoline having a specified distillation property and a specified component composition and excellent in smoldering performance, operability, and exhaust gas characteristics at low temperatures.

In recent years, fuel oils for gasoline engines have been demanded that have a high octane number and excellent driving performance as well as excellent environmental performance.
Conventionally, by blending methyl tertiary butyl ether (MTBE), which is a light and high-octane oxygen-containing base material described in Patent Document 1, carbon monoxide (CO) and total hydrocarbons (THC) can be reduced, Until recently, production and sales of gasoline with excellent low-temperature drivability were performed.
However, there is concern about the environmental impact of MTBE. At present, production and sales of gasoline containing MTBE are restrained, and in order to compensate for the decrease in octane number, the base material is heavy and has a high aromatic content. Gasoline blended with has come to be produced.

In this case, as gasoline having a specific distillation property and component composition is known (see, for example, Patent Document 2), a high-octane base material having a heavy and high aromatic content is blended. Although the octane number of the water component is improved, there is a concern that the octane number of the low-boiling fraction is lowered, the gasoline is heavier, the smoldering property of the plug is reduced, and the driving performance is affected.
In order to improve the operability at such low temperatures, it is important to increase the octane number of the low-boiling fraction, and the lighter and higher octane number is effective for plug smoldering to satisfy that requirement. Examples thereof include oxygen-containing compounds having properties. As the oxygen-containing compound, for example, ethyl tertiary butyl ether (ETBE) and tertiary amyl methyl ether (TAME) (SAE 912313) are known in addition to the aforementioned methyl tertiary butyl ether (MTBE).
In addition, gasoline (SAE902132) mixed with oxygen-containing compounds such as alcohols and ethers is also known, but these gasolines may still not be satisfactory in terms of startability, operability, etc., and further improvements can be made. It is desired.
Japanese Patent Publication No. 5-53197 JP-A-7-207286

  It is an object of the present invention to provide unleaded gasoline for gasoline engines that has excellent smolderability of plugs at low temperatures, has low exhaust gases such as CO and THC, and has a high octane number, without reducing the drivability of automobiles. To do.

As a result of intensive studies to achieve the above object, the present inventors have selected ethyl tertiary butyl ether (ETBE), which is a light high octane base, and a specific amount of ethyl tertiary butyl ether (ETBE). By using other specific base material, the aromatic content in the fuel oil is suppressed, the smoldering property of the plug is improved, and further, the distillation property and composition are further specified, thereby providing gasoline with excellent performance. Has been found, and the present invention has been completed.
That is, the present invention is an unleaded gasoline having the following configuration, thereby achieving the object of the present invention.
1. (A) 1 to 25% by volume of ethyl tertiary butyl ether (ETBE),
(B) (b-1) Debenzene contact with a research octane number (RON) of 100 or more, a motor method octane number (MON) of 88 or more, a Reid vapor pressure (RVP) of 30 kPa or more, and a boiling point range of 30 to 200 ° C. 2 to 50% by volume of reformed gasoline, or (b-2) 2 to 15 debenzene light catalytic reformed gasoline having RON of 78 or more, MON of 70 or more, RVP of 85 kPa or more, and boiling point range of 26 to 80 ° C. % By volume, RON of 101 or more, MON of 89 or more, RVP of 3 kPa or more, debenzene heavy catalytic reforming gasoline having a boiling range of 90 to 200 ° C., 2 to 50% by volume, and (C) RON of 93 or more, MON is 81 or more, RVP is 90 kPa or more, and the boiling point range is 25 to 110 ° C. Light catalytic cracking gasoline contains 10 to 50% by volume, RON is 98 or more, MON is 8 As mentioned above, aromatic content is 45 volume% or less, olefin content is 25 volume% or less, benzene content is 1 volume% or less, sulfur content is 10 mass ppm or less, 50% distillation temperature (T50) Is 80 to 110 ° C., 70 ° C. distillate (E70) is 20 to 45% by volume, RVP is 71.5 to 93 kPa, and a gas-liquid ratio (V / L) at 60 ° C. is 51 to 70. Lead-free high-octane gasoline (hereinafter referred to as “Unleaded Gasoline I”).
2. Furthermore, (D) RON is 93 or more, MON is 90 or more, RVP is 40 kPa or more, boiling point range is 30 to 210 ° C., and C8 fraction contains 5 to 30% by volume of alkylate. The unleaded high octane gasoline according to 1 above (hereinafter referred to as “unleaded gasoline II”).
3. 2. The lead-free high-octane gasoline according to 1 above, wherein the light catalytic cracking gasoline has a reed vapor pressure of 90 to 110 kPa.

  The high-octane lead-free gasoline of the present invention is used for automobile gasoline engines, improves the smoldering property of plugs at low temperatures, and can reduce the content of harmful components in exhaust gases such as CO and THC, Excellent low temperature startability, operability and high temperature restartability.

Hereinafter, the contents of the present invention will be described in more detail.
The unleaded high octane gasoline I of the present invention contains components (A), (B) and (C) as essential components. The unleaded high octane gasoline II contains the component (D) as an essential component in addition to the components (A) to (C).
Component (A) ethyl tertiary butyl ether (ETBE) is obtained as a reaction product of ethanol and isobutylene, and preferably has a purity of 95.0% or more.

  Component (B) Component (b-1) Debenzene-catalyzed reformed gasoline is obtained by converting heavy straight-run naphtha or the like into a catalytic reforming method (a platform forming method, a magna forming method, an aromaizing method, a reny forming method, a food reforming method). Obtained by contact treatment with a catalyst (for example, an alumina carrier carrying platinum, rhodium and chlorine) under high temperature and pressure in a hydrogen stream by a forming method, ultraforming method, power forming method, etc. The benzene fraction is removed from the reformed gasoline by distillation. In the present invention, RON is 100 or more, preferably 100 to 107, MON is 88 or more, preferably 88 to 95, RVP is 30 kPa or more, preferably 30 to 50 kPa, and the boiling point range is 30 to 200 ° C.

Moreover, the component (b-2) of a component (B) consists of debenzene light contact reforming gasoline and debenzene heavy contact reforming gasoline.
De-benzene light catalytic reforming gasoline is a method of catalytic reforming of heavy straight-run naphtha (Platforming method, Magnaforming method, Aromaizing method, Reniforming method, Food reforming method, Ultraforming method, Powerforming method) Etc.) by distilling the reformed gasoline obtained by contact treatment with a catalyst (for example, platinum carrier, rhodium and chlorine supported on an alumina carrier, etc.) in a hydrogen stream under high temperature and pressure. The light fraction is divided into benzene fraction and heavy fraction. The light fraction has a property that RON is 78 or more, preferably 78 to 90, MON is 70 or more, preferably 70 to 83, RVP is 85 kPa or more, preferably 85 to 105 kPa, and a boiling point range is 26 to 80 ° C. .
The debenzene heavy contact reformed gasoline is a heavy fraction of the reformed gasoline divided into a light fraction, a benzene fraction and a heavy fraction by distillation. The heavy fraction has a property that RON is 101 or more, preferably 101 to 110, MON is 89 or more, preferably 89 to 98, RVP is 3 kPa or more, preferably 3 to 15 kPa, and a boiling range is 90 to 200 ° C. .

  The light catalytic cracking gasoline of component (C) is a conventional catalytic cracking method, particularly a fluid catalytic cracking method, in which a petroleum fraction from kerosene / light oil to atmospheric residual oil, preferably heavy gas oil or vacuum gas oil is known. (UOP method, shell two-stage method, flexi cracking method, ultra ortho flow method, texaco method, Gulf method, ultra cat cracking method, RCC method, HOC method, etc.), solid acid catalyst (for example, silica / alumina with zeolite It is a light component obtained by distilling catalytic cracked gasoline obtained by cracking with a blend of The light catalytic cracking gasoline used in the present invention has RON of 93 or more, preferably 93 to 97, MON of 81 or more, preferably 81 to 85, RVP of 90 kPa or more, preferably 90 to 110 kPa, and a boiling range of 25 to 110. It has the property of ° C.

  The component (D) alkylate is obtained by reacting isobutane and a lower olefin (butene, propylene, etc.) as raw materials in the presence of an acid catalyst (sulfuric acid, hydrogen fluoride, aluminum chloride, etc.). In the present invention, various alkylates having a C8 fraction of 65% by volume or more, preferably 70% by volume or more are used. The alkylate used contains 28% by volume or more, preferably 30% by volume or more of isooctane (2,2,4-trimethylpentane). The alkylate has a property that RON is 93 or more, preferably 94 to 96, MON is 90 or more, preferably 91 to 94, RVP is 40 kPa or more, and a boiling point range is 30 to 210 ° C. Such an alkylate, i.e., unleaded gasoline II containing component (D), has a reduced difference between RON and MON and improved sensitivity (RON-MON).

  The unleaded gasoline I of the present invention has components (A), (B) and (C), the unleaded gasoline II has components (A), (B), (C) and (D) as essential components, What is necessary is just to select suitably according to the property of each component, etc. so that the required property of the fuel oil mentioned above may be satisfied.

Unleaded high-octane gasoline I usually has 1 to 25% by volume, preferably 3 to 20% by volume of ETBE, which is component (A), and debenzene-catalyzed reformed gasoline that is component (b-1) of component (B). 2 to 50% by volume, preferably 5 to 45% by volume, or 2 to 15% by volume of debenzene light catalytic reforming gasoline constituting component (b-2) of component (B), debenzene heavy catalytic reforming Quality gasoline may be blended as appropriate in the range of 2 to 50% by volume, preferably 10 to 50% by volume, and light catalytic cracking gasoline of component (C) in the range of 10 to 50% by volume, preferably 10 to 45% by volume. .
The unleaded high octane gasoline II has 5-30% by volume, preferably 5-25% by volume, of the above-mentioned unchelated high octane gasoline I components (A), (B), (C) and the component (D) alkylate. What is necessary is just to mix | blend suitably in the range.
In the case where the ETBE of the component (A) exceeds 25% by volume, there is a concern about the influence on the fuel consumption due to the decrease in the calorific value.

The lead-free high octane gasolines I and II containing the above components have RON of 98 or more, preferably 98 to 102, MON of 86 or more, preferably 86 to 90, and aromatic content of 45% by volume or less, preferably Is 40 volume% or less, olefin content is 25 volume% or less, preferably 20 volume% or less, T50 is 80 to 110 ° C., preferably 80 to 105 ° C., E70 is 20 to 45 volume%, preferably 20 to 40%. % By volume, RVP is 44 to 93 kPa, preferably 50 to 90 kPa, V / L at 60 ° C. is 30 to 70, preferably 35 to 60, benzene content is 1% by volume or less, and sulfur content is 10 It has properties of mass ppm or less.
If the aromatic content of the unleaded high-octane gasolines I and II exceeds the above range, there is a possibility that smoldering of the plug may occur or harmful components in the exhaust gas may increase. Moreover, when the olefin content exceeds the above range, NOx in the exhaust gas may increase when the oxidation stability is poor, which is not preferable.
Further, if T50, E70, RVP, or V / L at 60 ° C. is outside the above range, problems may occur in startability, acceleration, and drivability, which is not preferable.
Further, if the benzene content exceeds 1% by volume, the concentration of benzene in the exhaust gas may increase, and if the sulfur content exceeds 10 mass ppm, the exhaust gas purification performance may be affected.

  RON is based on JIS K 2280, aromatic content, olefin content, and benzene are based on the Petroleum Institute method JPI-5S-33-90 (gas chromatography method), and distillation properties such as T50 and E70 are In accordance with JIS K 2254, RVP is in accordance with JIS K 2258, V / L at 60 ° C. is in accordance with ASTM D 2533-93a, and the sulfur content is a value measured in accordance with JIS K 2541. .

  The unleaded high octane gasolines I and II of the present invention can be appropriately mixed with various additives as necessary. Such additives include phenolic and amine antioxidants, metal deactivators such as thioamide compounds, surface ignition inhibitors such as organophosphorus compounds, succinimides, polyalkylamines, polyetheramines. Detergents such as polyisobutylene amine, anti-freezing agents such as polyhydric alcohols and ethers thereof, organic metal alkali metal and alkaline earth metal salts, auxiliary alcohols such as higher alcohol sulfates, anionic surfactants, Known fuel additives include antistatic agents such as cationic surfactants and amphoteric surfactants, rust inhibitors such as alkenyl succinates, and colorants such as azo dyes. These can be added singly or in combination. The addition amount of these fuel additives is arbitrary, but usually the total addition amount is preferably 0.1% by mass or less.

  Furthermore, if necessary, the fuel oil composition of the present invention can be obtained by distilling butane and butenes obtained by distillation during atmospheric distillation of crude oil, crude oil, etc., during the production of reformed gasoline, or during the production of cracked gasoline. Is obtained by isomerization of a C4 fraction having a main component, straight chain lower paraffin hydrocarbons, light naphtha, preferably obtained from desulfurized light naphtha, reformed gasoline, etc., or isomerate is subjected to precision distillation. It is also possible to blend isopentane obtained in this manner, toluene, xylene obtained from an aromatic production facility, or an aromatic having 9 or more carbon atoms.

The content of the present invention will be described in more detail with reference to Examples , Comparative Examples and Reference Examples, but the present invention is not limited thereto.
( Reference Example 1, Examples 2 and 4)
C4 fraction (butane, butenes) produced from catalytic cracking equipment, catalytic reforming equipment or atmospheric distillation equipment, debenzene light catalytic reforming gasoline, debenzene heavy catalytic reforming gasoline, light catalytic cracking gasoline of the following properties , Alkylate, and ETBE were blended at the blending ratios shown in Table 1 to obtain gasoline having properties described in Table 1.
・ Debenzene light catalytic reformed gasoline 1.1% by volume of aromatics, 1.7% by volume of olefins, T50 of 45.0 ° C., E70 of 100% by volume, RVP of 102.5 kPa, and RON of 86%. 3, MON is 79.2
・ Debenzene heavy catalytic reformed gasoline Aromatic content is 88.2 vol%, olefin content is 0.4 vol%, T50 is 123.0 ° C, E70 is 0.0 vol%, RVP is 7.0 kPa, RON 103.9, MON 91.5
-Light catalytic cracked gasoline 1.2% by volume of aromatics, 44.3% by volume of olefins, 48.5 ° C. for T50, 91.5% by volume of E70, 105.0 kPa for RVP, 93.7 for RON MON is 81.7
・ Alkylate 0.2% by volume of aromatic content, 0.0% by volume of olefin, T50 of 106.0 ° C, E70 of 8.5% by volume, RVP of 48.0 kPa, RON of 94.6, MON Is 91.9

(Example 3)
C4 fraction (butane, butenes), light catalytic cracking gasoline, alkylate, ETBE and debenzene catalytic reforming gasoline of the following properties described in Reference Example 1 and Examples 2 and 4 were blended in the blending ratio shown in Table 1. As a result, gasoline having the properties shown in Table 1 was obtained.
・ Debenzene-catalyzed reformed gasoline Aromatic content is 70.8 vol%, olefin content is 0.9 vol%, T50 is 124.0 ° C, E70 is 10.0 vol%, RVP is 41.5 kPa, RON is 102 .2, MON is 90.0

( Reference Example 5)
Table 1 shows C4 fractions (butane, butenes), debenzene light catalytic reformed gasoline, debenzene heavy catalytic reformed gasoline, light catalytic cracked gasoline, and ETBE described in Reference Example 1, Examples 2 and 4. By blending at the blending ratio shown, gasoline having the properties shown in Table 1 was obtained.

(Comparative Example 1)
C4 fractions (butane, butenes), debenzene heavy catalytic reformed gasoline, light catalytic cracked gasoline, and alkylate described in Reference Example 1, Examples 2 and 4 were blended according to the description in Table 1, Table 1 Gasoline having the properties described in 1) was obtained.

(Comparative Example 2)
By blending the debenzene light catalytic reformed gasoline, the debenzene heavy catalytic reformed gasoline, and the light catalytic cracked gasoline described in Reference Example 1, Examples 2 and 4, gasoline having the properties described in Table 1 was obtained.

(Comparative Example 3)
The debenzene heavy catalytic reformed gasoline, light catalytic cracked gasoline, and alkylate described in Reference Example 1 and Examples 2 and 4 were blended according to the description in Table 1, and gasoline having the properties described in Table 1 was obtained.

Various performance evaluation tests described below were conducted using the gasolines of Examples 2 to 4 , Comparative Examples 1 to 3, and Reference Examples 1 and 5 . The method is described below, and the results are shown in Table 1.

(Plug smoldering test)
Using a vehicle with a total displacement of 2L, MPI method, automatic transmission (AT), and a test temperature condition of -10 ° C, about 30 minutes per cycle (engine start ⇒ 10-20 km / h acceleration / deceleration repeated 10 times ⇒ 28 The degree of fouling of the plug was measured by measuring the insulation resistance of the plug. It was determined that plug smoldering occurred when the plug insulation resistance value was 100 MΩ or less.

(Low temperature startability test)
Using a typical domestic passenger car (total displacement 1.5L, MPI system, automatic transmission (AT)), start the engine at ambient temperature (room temperature, oil temperature) -10 ° C, complete explosion time (cranking) After that, the time until the engine can continue to rotate by itself was measured.

(Acceleration test and high temperature restartability test)
A typical domestic passenger car (total displacement 1.5L, MPI system, automatic transmission (AT)) was used in accordance with CRC Report No.490.
Here, in the acceleration test, the time (acceleration time) from 40 km / h to 120 km / h was measured, and the acceleration time increase rate was obtained using the following formula (1).
In the high temperature restartability test, the starting time after key-off soak was measured.
Acceleration time increase rate (%) = [(Acceleration time after key-off soak (sec) −Reference acceleration time (sec)) / Reference acceleration time (sec)] × 100 Equation (1)

(Exhaust gas test)
Using domestic passenger cars (total displacement 2.5L, MPI system, automatic transmission (AT), three-way catalyst installed), exhaust gas test in 10.15 mode, carbon monoxide (CO), all hydrocarbons (THC) and nitrogen oxides (NOx) were measured.

  From the results shown in Table 1, the lead-free high-octane gasoline of the present invention has improved smoldering property of the plug at low temperatures, reduced content of harmful components in the exhaust gas of CO, THC, NOx, and excellent It turns out that it has low temperature startability, acceleration property, and high temperature restartability.

Claims (3)

(A) 1 to 25% by volume of ethyl tertiary butyl ether,
(B) (b-1) 2-50% by volume of debenzene contact reformed gasoline having a research octane number of 100 or more, a motor method octane number of 88 or more, a reed vapor pressure of 30 kPa or more, and a boiling point range of 30 to 200 ° C. Or (b-2) 2 to 15% by volume of debenzene light catalytic reformed gasoline having a research octane number of 78 or higher, a motor octane number of 70 or higher, a Reid vapor pressure of 85 kPa or higher, and a boiling point range of 26 to 80 ° C. Research method octane number of 101 or more, motor method octane number of 89 or more, reed vapor pressure of 3 kPa or more, boiling point range of 90-200 ° C debenzene heavy catalytic reformed gasoline 2-50% by volume, and (C) research method Light with an octane number of 93 or higher, motor method octane number of 81 or higher, Reed vapor pressure of 90 kPa or higher, and boiling range of 25 to 110 ° C Contains 10-50% by volume of catalytic cracking gasoline, research method octane number is 98 or more, motor method octane number is 86 or more, aromatic content is 45% by volume or less, olefin content is 25% by volume or less, benzene content is 1% by volume or less, sulfur content is 10 mass ppm or less, 50% distillation temperature is 80 to 110 ° C., 70 ° C. distillation amount is 20 to 45% by volume, Reed vapor pressure is 71.5 to 93 kPa, and 60 A lead-free high-octane gasoline having a gas-liquid ratio (V / L) at 51 ° C. of 51 to 70.   Furthermore, (D) 5 to 30 volumes of alkylate having a research octane number of 93 or more, a motor method octane number of 90 or more, a Reid vapor pressure of 40 kPa or more, a boiling range of 30 to 210 ° C., and a C8 fraction of 65 vol% or more. The unleaded high octane gasoline according to claim 1, comprising: The lead-free high-octane gasoline according to claim 1, wherein a lead vapor pressure of the light catalytic cracking gasoline is 90 to 110 kPa.