JP2007126504A - Etbe-containing gasoline composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an ethyl tertiary-butyl ether-containing gasoline composition having excellent rust prevention performance and cold-engine driveability and to provide a method for producing the same. <P>SOLUTION: The ETBE-containing gasoline composition has 1-20 vol.% ethyl tertiary butyl ether (ETBE) content, ≤3.0 vol.% ≤7C aromatic hydrocarbon content and the ratio (volume ratio) of (9C aromatic hydrocarbon content)/(7C aromatic hydrocarbon content) of ≥3 and the drivability index represented by the formula: A=5×(T10)+6×(T50)+(T70)+30×(OX) (T10 is 10% distillation temperature(°C); T50 is 50% distillation temperature(°C); T70 is 70% distillation temperature(°C); OX is an oxygen content (mass%)) of ≤1,020. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a gasoline composition containing ethyl tertiary butyl ether (ETBE), and in particular, to a gasoline composition excellent in rust prevention performance and cold-time drivability, and a method for producing the same.

It has been reported that increasing the octane number of regular gasoline using ethanol or ethyl tertiary butyl ether (hereinafter referred to as ETBE), which are oxygenated compounds, increases the thermal efficiency of the engine and contributes to CO ₂ reduction (non-patented) Reference 1). Among them, ETBE has a higher octane number at the same oxygen content than ethanol, and does not cause an increase in vapor pressure due to an azeotropic phenomenon even at a low addition amount, and causes phase separation of gasoline when mixed with water. It is easy to handle because it does not occur. In view of these advantages and the CO ₂ reduction effect, it has been decided to introduce it into gasoline in 2010. In addition, there are many gasoline production methods that improve operability, acceleration, and exhaust gas by mixing ETBE containing gasoline with ETBE as a base material for improving octane number (Patent Document 1) and ETBE mixed with gasoline. It has been reported (Patent Document 2, Patent Document 3). However, when increasing the octane number of regular gasoline using ETBE, if ETBE is mixed, the rust prevention performance of the gasoline will be reduced and the drivability will be deteriorated when the engine is cold. There are no reports.
JP 2005-029762 A JP 2004-292511 A JP 2004-285204 A JCAP 4th Results Presentation "Gasoline WG Report-Sulfur Content, Octane Number Test Results-" Gasoline WG, Japan Petroleum Industry Activation Center, 2005.6.1, Internet <URL: http: // www. pecj.or.jp/japanese/jcap/pdf/JCAP200506/2_1.pdf>

  In gasoline blended with ETBE, the rust prevention performance deteriorates due to ETBE, and the operability during cold operation may not be good. An object of the present invention is to solve such problems, and to provide an ETBE-containing gasoline composition having excellent rust prevention performance and cold-time operability while being a gasoline composition containing ETBE, Furthermore, it is an object to provide a manufacturing method thereof.

The ETBE-containing gasoline composition according to the present invention has an ETBE content of 1 to 20% by volume, a C7 aromatic hydrocarbon content of 3.0% by volume or less, and a (C9 aromatic carbonization). The gasoline composition has a hydrogen content) / (aromatic hydrocarbon content of 7 carbon atoms) ratio (capacity ratio) of 3 or more and an operation index A represented by the following formula of 1020 or less.
A = 5 × (T10) + 6 × (T50) + (T70) + 30 × (OX)
In the formula, T10 represents a 10% distillation temperature (° C), T50 represents a 50% distillation temperature (° C), T70 represents a 70% distillation temperature (° C), and OX represents an oxygen content (% by mass).

The gasoline composition of the present invention has a sulfur content of 10 mass ppm or less, an (ethanol content) / (ETBE content) ratio (volume ratio) of 0.001 to 0.010, and research. It is a gasoline composition having a legal octane number of 91 to 98. Moreover, it is preferable that the antirust agent is added.
Moreover, what contains TBA so that (tertiary butyl alcohol (henceforth TBA) content) / (ETBE content) ratio (capacity ratio) may be 0.004-0.010 is preferable.

  The gasoline composition of the present invention has an (n-C7 + n-C8) / (n-C9 + n-C10) ratio (volume ratio) of 3 or less obtained from catalytic cracked gasoline, and (n-C7 + n-C8) / What contains 50-80 volume% of the catalytic cracking gasoline base material whose (n-C5 + n-C6) ratio (volume ratio) is 0.5 or less is preferable. In addition, about the symbol showing the said volume ratio, n-C5 is n-pentane content (volume%), n-C6 is n-hexane content (volume%), n-C7 is n-heptane content (volume%). N-C8 represents n-octane content (volume%), n-C9 represents n-nonane content (volume%), and n-C10 represents n-decane content (volume%).

  The manufacturing method of the ETBE containing gasoline composition by this invention mix | blends a hydrocarbon base material and an ETBE base material, and manufactures the above-mentioned ETBE containing gasoline composition.

  Further, ETBE having a purity of 90 to 98% by volume is distilled and separated to obtain a high purity ETBE having an ETBE purity of 99% by volume or more and a low purity ETBE having a purity of less than 98% by volume, and the low purity ETBE is used as an ETBE base material. preferable.

  The ETBE-containing gasoline composition according to the present invention limits the content of aromatic hydrocarbons having 9 carbon atoms and the content of aromatic hydrocarbons having 7 carbon atoms to specific ranges, and is further calculated from distillation properties and oxygen content. Because it is an ETBE-containing gasoline composition that limits the operability index A to be within a predetermined range, it has a sufficient anti-corrosion performance while containing ETBE and exhibits good cold-time operability Exerts a positive effect.

The gasoline composition containing ETBE according to the present invention contains 1 to 20% by volume of ETBE. The ETBE content is preferably 5% by volume or more, more preferably 7% by volume or more, and particularly preferably 10% by volume or more from the effect of improving the octane number. On the other hand, it is preferably 20% by volume or less from the viewpoint of fuel consumption, more preferably 17% by volume or less, and particularly preferably 15% by volume or less from the viewpoints of rust prevention performance, water separation and the like.
The content of aromatic hydrocarbons having 7 carbon atoms is 3.0% by volume or less, preferably 2.5% by volume or less, more preferably 2.0% by volume or less, particularly 1.5% by volume or less in terms of rust prevention performance. is there. Further, it is preferably 0.1% by volume or more from the standpoint of cold operation.

  Further, the ratio (capacity ratio) of the aromatic hydrocarbon content of 9 carbon atoms to the aromatic hydrocarbon content of 7 carbon atoms is 3 or more, preferably 5 or more, more preferably 10 from the rust prevention performance. Above, especially 20 or more.

Furthermore, the driveability index A represented by the following formula is 1020 or less.
A = 5 × (T10) + 6 × (T50) + (T70) + 30 × (OX)
In the formula, T10 represents a 10% distillation temperature (° C), T50 represents a 50% distillation temperature (° C), T70 represents a 70% distillation temperature (° C), and OX represents an oxygen content (% by mass).
The drivability index A is preferably 1010 or less, more preferably 1000 or less, and particularly 990 or less from the viewpoint of drivability during cold operation.

The sulfur content in the ETBE-containing gasoline composition is preferably 10 ppm by mass or less, and more preferably 5 ppm by mass or less in order to avoid sulfur poisoning of the exhaust gas purification catalyst.
Further, the ratio of ethanol content to ETBE content (volume ratio) is preferably 0.001 to 0.010, more preferably 0.0015 or more, and still more preferably 0 from the viewpoint of rust prevention performance and water fog prevention performance. 0020 or more. On the other hand, it is preferably 0.009 or less, more preferably 0.008 or less, in order to avoid deterioration of water separability and decrease in octane number per oxygen content. It is preferable that this ethanol is contained in ETBE at the time of ETBE production because it reduces the purification cost. However, after the ETBE production, ethanol may be mixed with gasoline so as to be within the preferred range.
The research-method octane number (hereinafter simply referred to as octane number or RON) possessed by the ETBE-containing gasoline composition of the present invention is preferably 91 to 98, and is 93 or more, more preferably 95 or more, because it increases the thermal efficiency of the engine. On the other hand, since the distillation property may become heavy by increasing the octane number or the operability during cold operation may be deteriorated, 97 or less is preferable, and 96 or less is more preferable.
The ETBE-containing gasoline composition of the present invention contains TBA as an alcohol other than ethanol so that the ratio (volume ratio) of (TBA content) / (ETBE content) is 0.004 to 0.100. In view of rust prevention performance, 0.006 or more is more preferable. From the viewpoint of lowering the octane number and increasing the vapor pressure, the TBA content is preferably 0.010 or less, more preferably 0.009 or less, and particularly preferably 0.09 or less, and the (TBA content) / (ETBE content) ratio. 008 or less.

Moreover, it is preferable that the ETBE containing gasoline composition of this invention contains the antirust agent. As rust preventives, inorganic chromate, sodium tungstate, sodium molybdate, vanadate, nitrite, benzoate, silicate, borate, phosphate, organic, amine, pyridine, Nitrogen-containing compounds such as quaternary pyridine base salts, sulfur-containing compounds such as 2-mercaptoimidazole and propargyl alcohol, acetylene compounds such as hexyne-1-ol-3, propargyl ester, and the like, in particular, carboxylic acid ester fatty acid amines Alkenyl succinate phosphates and phosphite esters of alkylphenols are preferred. The content of the rust inhibitor is usually 1 to 50 mg / l, but preferably 1 to 10 mg / l. It may contain a metal deactivator. In this case, it contains 1-2 mg / L of NN'-disalicylidene, 1,2-propanediamine, etc., which are usually used in jet fuel. It is preferable to make it.
Although these rust inhibitors and metal deactivators can be added to gasoline alone, they are usually sold as products packaged with detergents such as polyisobuteneamine and polyetheramine. When adding to gasoline, the package additive with detergent is usually added in an amount of 50 to 300 mg / l so that the unwashed real gum (JIS K2261) of the additive-added gasoline satisfies 20 mg / 100 ml or less. .

The ETBE-containing gasoline composition of the present invention has a (n-C7 + n-C8) / (n-C9 + n-C10) ratio (volume ratio) of 3 or less obtained from catalytically cracked gasoline, and (n-C7 + n-C8). ) / (N-C5 + n-C6) ratio (volume ratio) is preferably 50 to 80% by volume of a catalytically cracked gasoline base material having a ratio of 0.5 or less. A catalytically cracked gasoline base material satisfying this formula is preferable as a gasoline base material because of its relatively high octane number. Since the catalytic cracking gasoline base has a lower production cost than the aromatic base, it is more preferably 60% by volume or more, particularly preferably 65% by volume or more, and also prevents the decrease in octane and heavy distillation properties. In view of this, it is preferably 78% by volume or less, particularly preferably 75% or less.
The (n-C7 + n-C8) / (n-C9 + n-C10) ratio (capacity ratio) is 3 or less, and the (n-C7 + n-C8) / (n-C5 + n-C6) ratio (capacity ratio) is The method for preparing the catalytic cracking gasoline base material of 0.5 or less is not particularly limited. For example, the catalytic cracking gasoline produced by the various production processes and purification processes described below is fractionated to obtain a light A fraction, a medium fraction and a heavy fraction can be obtained, and the light fraction and the heavy fraction can be obtained by mixing so as to satisfy the above ratio (volume ratio) of normal paraffin components.

  The method for producing an ETBE-containing gasoline composition according to the present invention comprises a gasoline base material (hereinafter referred to as hydrocarbon base material) composed of a mineral oil-based and / or synthetic oil-based hydrocarbon compound, and a commercially available ETBE product for gasoline preparation. ETBE obtained by synthesizing ethanol and isobutylene, or obtained by dehydration reaction of ethanol and TBA, and further, fractionating and purifying them to appropriately adjust the ETBE purity, impurity content, etc. The above-described ETBE-containing gasoline composition is produced by blending a gasoline base material containing ETBE as a main component (hereinafter referred to as ETBE base material).

The ETBE base material used in the production method of the present invention preferably contains TBA as an alcohol other than ethanol so that the ratio (TBA content) / (ETBE content) is 0.004 to 0.100. In view of rust prevention performance, 0.006 or more is more preferable. From the viewpoint of decreasing the octane number or increasing the vapor pressure, the TBA content is preferably (TBA content) / (ETBE content) ratio of 0.010 or less, more preferably 0.009 or less, and particularly 0.008. It is as follows. As the ETBE base material, a commercially available product (for example, ETBE manufactured by Chevron Chemical having a purity of about 95%) can be used as it is, but it is not preferable to use it as it is because there is a product having inferior rust prevention performance. Relatively low-purity ETBE is preferably used separately by distillation into high-purity ETBE of 99% or more and low-purity ETBE of less than 98% ETBE. The ETBE-containing gasoline composition of the present invention can be used with either high purity ETBE or low purity ETBE. Ethanol and TBA, which improve rust prevention performance, are relatively contained in light fractions (low purity ETBE) when they are separated by distillation. For this reason, blending this light fraction so as to fall within the above preferred range is effective for imparting rust prevention performance while suppressing a decrease in octane number and an increase in vapor pressure. When TBA is used as an ETBE synthesis raw material, it is preferable that TBA is contained in the ETBE base material from the viewpoint of reducing the purification cost. However, even if TBA itself is included in the above preferable range, good.
In addition, it is also effective to add an anticorrosive agent to the ETBE-containing gasoline composition of the present invention.

Further, high purity ETBE having a purity of 99% by volume or more obtained by distilling and separating commercially available ETBE is mixed with gasoline having a relatively high octane number and containing a rust inhibitor (so-called premium gasoline). It is possible to mix high purity ETBE and low purity ETBE without waste by mixing ETBE of less than 98% by volume of low purity ETBE produced as a residue obtained by distillation separation of ETBE into the ETBE-containing gasoline composition having a relatively low octane number of the present invention. This is preferable because it is used in the manufacture of
As the ETBE base material used in the production method of the present invention, an ETBE base material that matches the target quality may be accepted from inside and outside the country, and the ETBE base material that is manufactured, separated, or purified according to the target quality at home and abroad is used. May be. This ETBE base material is usually blended in an amount of 1 to 20% by volume in the production of the ETBE-containing gasoline composition of the present invention.

  In addition, as ethanol, which is a raw material for ETBE synthesis, the use of bioethanol produced from excess production of corn, sugarcane, or waste cellulose, etc., prevents the increase in carbon dioxide. From the viewpoint of In addition, as isobutene, which is another raw material for ETBE synthesis, it is preferable that the content of hydrocarbon compounds having 3 or less carbon atoms and 5 or more carbon atoms is smaller because fewer by-products are produced during ETBE production.

  The sulfur content of the ETBE base material used in this ETBE-containing gasoline composition is preferably 5 mass ppm or less, more preferably 2 mass ppm or less, and particularly preferably 1 mass ppm or less from the viewpoint of preventing catalyst poisoning of exhaust gas. . In addition, the lead vapor pressure of the ETBE base material is preferably 40 kPa or less, more preferably 37 kPa or less, and particularly preferably 35 kPa or less from the effect of reducing the gasoline vapor pressure.

Further, from the viewpoint of reducing the vapor pressure of gasoline, the content of hydrocarbon compounds having 4 or less carbon atoms is preferably 1% by volume or less, more preferably 0.5% by volume or less, and particularly preferably 0.1% by volume or less. In view of the effect of reducing the boiling point, the content of the hydrocarbon compound having 8 or more carbon atoms is preferably 1% by volume or less, more preferably 0.5% by volume or less, and particularly preferably 0.1% by volume or less.
The olefin content is preferably 0.5% by volume or less, more preferably 0.1% by volume or less, from the viewpoint of oxidation stability.

  Further, from the viewpoint of preventing deterioration of exhaust gas quality, the benzene content is preferably 0.5% by volume or less, more preferably 0.2% by volume or less, and particularly preferably 0.1% by volume or less. Further, the toluene content is preferably 5% by volume or less, more preferably 4% by volume or less, and particularly preferably 3% by volume or less, from the suppression of boiling point rise and rust prevention performance. Further, in order to prevent separation of the aqueous layer due to water mixing, methyl tertiary butyl ether (MTBE) is preferably 0.3% by volume or less. Furthermore, it is preferably 0.2% by volume or less, particularly 0.1% by volume or less. Further, from the viewpoint of preventing water fogging, the water content is preferably 500 mass ppm or less, more preferably 400 mass ppm or less, and particularly preferably 350 mass ppm or less.

[Catalytic cracking gasoline base material]
Although the catalytic cracking gasoline base material is one of the hydrocarbon base materials described later, it is the most important base material constituting the ETBE-containing gasoline composition of the present invention.
The production process of the catalytic cracking gasoline is not particularly limited to the catalytic cracking apparatus, the raw material oil, and the operating conditions, and any known production process can be adopted. The catalytic cracking unit uses a catalyst such as amorphous silica alumina, zeolite, etc., in addition to petroleum fractions from light oil to vacuum gas oil, while being obtained from heavy oil indirect desulfurization unit, it can be obtained directly from degassing oil or heavy oil direct desulfurization unit. This is a device that obtains a high octane gasoline base material by catalytic cracking of degassed oil, atmospheric residue oil and the like. For example, UOP catalytic cracking method, flexi cracking method, ultra-orthoflow method, fluid catalytic cracking method such as Texaco fluid catalytic cracking method, RCC method, HOC method, etc. Examples include fluid catalytic cracking. In order to reduce the sulfur content of the catalytic cracking gasoline, it is preferable to reduce the sulfur content of the raw material oil applied to the catalytic cracking apparatus as much as possible or to desulfurize the catalytic cracking gasoline itself. In order to desulfurize catalytically cracked gasoline, it is preferable to desulfurize while suppressing the decrease in octane number as much as possible. The desulfurization methods include ExxonMobil's SCANfining process, Axens' Prime-G + process, and UOP's ISAL process. (21st JPI Petroleum Refining Conference "Recent Progress in Petroleum Process Technology" 2002)

  The catalytic cracking gasoline base material has an (n-C7 + n-C8) / (n-C9 + n-C10) ratio (volume ratio) of 3 or less and an (n-C7 + n-C8) / (n-C5 + n-C6) ratio (capacity). It is preferable that the catalytically cracked gasoline is fractionally distilled so that the ratio) is 0.5 or less, each fraction is appropriately selected, mixed and adjusted. More preferably, the (n-C7 + n-C8) / (n-C9 + n-C10) ratio (capacity ratio) is 2 or less, particularly 1 or less, and the (n-C7 + n-C8) / (n-C5 + n-C6) ratio It is preferable that the catalytically cracked gasoline is fractionally distilled so that (volume ratio) is 0.4 or less, each fraction is appropriately selected, mixed and adjusted. Thereby, the octane number can be improved with almost no change in distillation properties.

[Hydrocarbon substrate]
As an important hydrocarbon base material other than the catalytic cracking gasoline base material, firstly, a reformed gasoline base material is exemplified. In order to achieve the effect of the present invention when using a reformed gasoline base material, the reformed gasoline is separated into 7 to 9 or more carbon atoms at each carbon number, and among these, a base material having 9 or more carbon atoms, so-called heavy modification. It is preferable to use quality gasoline (sometimes referred to as AC9). Heavy reformed gasoline (AC9) is a relatively heavy fraction of a catalytically reformed gasoline base material, mainly composed of a hydrocarbon compound having 9 carbon atoms, having a 10% distillation temperature of 150 ° C or higher. The fraction is preferably 155 to 170 ° C. This fraction contains an aromatic content of 90% by mass or more, particularly 95% by mass or more, and a 90% distillation temperature is preferably 165 to 175 ° C. Such heavy reformed gasoline is preferably blended in an amount of 5 to 25% by volume, particularly 10 to 20% by volume. As the reformate base material, in addition to AC9, a fraction mainly composed of a hydrocarbon compound having 7 to 8 carbon atoms (AC7 or AC8), or so-called reformed gasoline in a hole before distillation separation is appropriately used. It can be used as long as the effects of the present invention are not impaired.

  Further, other alkylate base materials obtained by alkylating isobutane and butylene mainly with sulfuric acid or a hydrogen fluoride catalyst can be preferably used. Furthermore, other hydrocarbon bases for gasoline preparation include straight-run naphtha obtained by atmospheric distillation of crude oil, desulfurized naphtha obtained by desulfurizing straight-run naphtha, and light naphtha by contact treatment and isomerization to increase the octane number. Examples thereof include rate (isomerized gasoline), LPG fraction recovered from crude oil and various secondary refining apparatuses, light naphtha, butane and isopentane (iC5) obtained by precision distillation thereof.

  Further, as the hydrocarbon substrate, a substrate mainly composed of aromatic hydrocarbons having 7 and 8 carbon atoms, that is, toluene and xylene can be used. These can typically be obtained by fractionating reformed gasoline. For example, a substrate containing 80% by volume or more of toluene can be blended in an amount of 10% by volume or less, more preferably 5% by volume or less. However, it is preferable not to mix the aromatic hydrocarbon base material from the viewpoint of environmental protection.

Further, in addition to the above hydrocarbon base and ETBE base, it is not particularly limited as a gasoline base, but methyl-t-butyl ether (MTBE), ethyl-s-butyl ether (ESBE), t-amyl ethyl ether (TAEE). ), Oxygen-containing gasoline base materials such as methanol and ethanol can be used.
A gasoline base such as a hydrocarbon base, an ETBE base, or an oxygen-containing gasoline base preferably has a sulfur content of 10 mass ppm or less, particularly preferably 5 mass ppm or less.

[Other additives]
Furthermore, in addition to the above-mentioned rust preventive agent, one or more fuel oil additives known in the art can be blended with the gasoline of the present invention as required. Although these compounding quantities can be selected suitably, it is preferable to maintain the total compounding quantity of an additive to 0.1 mass% or less normally. Examples of fuel oil additives that can be used in the gasoline of the present invention include phenolic, amine-based antioxidants, Schiff-type compounds, metal deactivators such as thioamide-type compounds, and organic phosphorus-based surfaces. 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 Examples include an auxiliary combustor such as an ester, an anionic surfactant, a cationic surfactant, an antistatic agent such as an amphoteric surfactant, and a colorant such as an azo dye.

  In particular, when the ETBE base material is inferior in oxidation stability, it is effective to add an antioxidant as appropriate depending on the amount mixed with gasoline. In Europe, 50 mass ppm or more may be added. Further, a detergent such as polyisobutylamine or polyetheramine is appropriately added to the ETBE base material in the range of 0 to 2000 mg / L in accordance with the gasoline mixing ratio of the ETBE base material and the unwashed actual gum tolerance of the gasoline. It is also effective. It is also effective to add a rust inhibitor and a metal deactivator in order to improve the rust prevention performance of the ETBE base material.

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

[Preparation of ETBE base material]
Precise distillation separation (separation conditions: number of theoretical plates 15, column top temperature 73 ° C., pressure 745 to 750 mmHg, reflux ratio 5) using ETBE base material manufactured by Chevron Chemical USA as a raw material, 30% light by weight, heavy content Was cut by 10% by volume, and about 55% by volume of high-purity ETBE having an ETBE purity of 99% by volume or more was obtained. Moreover, the ETBE purity of the cut light part was less than 98 volume%, and what added 2% of Brazilian bioethanol was used for the preparation of the gasoline composition of an Example and a comparative example. 100 mg / L of a detergent (AP114K manufactured by BASF) imparted with rust prevention performance was added to the above-described high-purity ETBE base material to prepare a detergent-added high-purity ETBE. Table 1 shows various properties of each ETBE base material.

[Preparation of gasoline composition]
Prepare gasoline base materials (hydrocarbon base materials) shown in Tables 2 and 3 and blend them at the mixing ratio (volume%) shown in the upper part of Tables 4 and 5 to provide gasoline compositions as examples and comparative examples. Prepared. The gasoline base material used was prepared as follows. Moreover, the used antirust agent used AP114K by BASF sold as a package product with a detergent, and the addition amount was 100 mg / L.

C4:
A so-called butane fraction was obtained by distilling and separating the desulfurized liquefied petroleum gas to obtain a fraction containing 95% or more of hydrocarbons having 4 carbon atoms and 73% by volume of normal butane.
iC5:
A fraction mainly containing 5 carbon atoms containing a large amount of isopentane was obtained by distilling and separating the desulfurized light naphtha fraction to obtain a 5 carbon component having a purity of 95% or more.
DS-LG:
Desulfurized straight-run light naphtha obtained by hydrodesulfurizing a naphtha fraction of Middle Eastern crude oil and distilling the light fraction.
ALKG:
Alkylate gasoline, a fraction containing butylene as a main component and a fraction containing isobutane as a main component were subjected to an alkylation reaction from a sulfuric acid catalyst to obtain a hydrocarbon having a high isoparaffin content.
FCCG:
Fluid catalytic cracking gasoline, after desulfurizing desulfurized gas oil and desulfurized heavy oil using a fluidized bed reactor with solid catalyst, selective hydrodesulfurization while suppressing olefin hydrogenation, sweetening, and olefin content A hydrocarbon (FCCG) having a high sulfur content and a low sulfur content was obtained.
FCCG-1:
FCCG-1 is fractionated into a light fraction of 40% by volume, a medium fraction of 25% by volume, and a heavy fraction of 35% by volume, and the resulting light fraction and heavy fraction are mixed together to obtain FCCG-1. Obtained.
FCCG-2:
Similar to FCCG-1, the above-mentioned FCCG is fractionated into 50% by light fraction, 27% by volume of medium fraction and 23% by volume of heavy fraction, and the resulting light fraction and heavy fraction are separated. Mixing to obtain FCCG-2.
TOL:
Toluene with a purity of 99.5% by volume. When obtaining the desulfurized straight-run light naphtha (DS-LG), after desulfurization, the heavy fraction (desulfurized heavy naphtha) is distilled and separated. This desulfurized heavy naphtha was reformed with a solid catalyst using a moving bed reactor to obtain a hydrocarbon with a high aromatic content, that is, reformed gasoline. From this, the aromatic component was extracted using a sulfolane solvent, and then the extracted aromatic component was separated by distillation to obtain a fraction containing 99.5% by volume of toluene.
AC9:
It is a heavy reformed gasoline, and in the distillation separation of the reformed gasoline prepared as described above, hydrocarbons having 11 or more carbon atoms are contained in 5% by volume or less, and hydrocarbons having 9 or 10 carbon atoms in 90% by volume or more. Fraction (AC9) was obtained. The content of aromatic hydrocarbon having 9 carbon atoms is 90% by volume.
ethanol:
Brazilian bioethanol. The ethanol purity is 99.0% and the water content is 5,800 ppm by mass.

The lower part of Tables 4 and 5 shows the evaluation test results of the physical properties and performance of the gasoline compositions of the examples and comparative examples prepared and prepared.
The properties of the gasoline compositions of ETBE base materials, gasoline base materials and examples and comparative examples shown in Tables 1 to 5 were measured by the following methods.
Distillation properties: JIS K 2254 "Petroleum products-Distillation test method"
Vapor pressure (RVP): JIS K 2258 "Crude oil and fuel oil-Vapor pressure test method-Reed method"
Octane number (RON): JIS K 2280 "Petroleum products-Fuel oil-Octane number and cetane number test method and cetane index calculation method" research method Octane number test method Sulfur content: JIS K 2541 "Crude oil and petroleum products-Sulfur content test method" In accordance with the ultraviolet fluorescence method (ASTM D 5453 (ultraviolet fluorescence method)).
Nitrogen content: JIS K 2606 “Testing method for nitrogen content (chemiluminescence method)
Density: JIS K 2249 "Crude oil and petroleum products-Density test method"
Moisture: measured by the Karl Fischer method.

Olefin, aromatic, normal paraffin (n-C5 to n-C10), benzene, aromatics having 7 or 9 carbon atoms (toluene, AC7, AC9), hydrocarbon compound content: JIS K 2536 "Petroleum products-components The measurement was performed under the following conditions by the gas chromatography method of “Test Method”.
[Column tank conditions]
Material: methyl silicone 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
Diene number: According to UOP method 326-82, the number of grams of iodine equivalent to maleic anhydride reacting with 100 g of sample was determined. Both compounds detected by the diene number are contained in a large amount in catalytically cracked gasoline and pyrolyzed gasoline and have a specific odor. In particular, when the diene number is high, the oxidation stability of gasoline is deteriorated.

ETBE content and content of impurities such as alcohol and ether having 2 or more carbon atoms: measured by GC-MS and GC-FID. The measurement conditions are as follows.
[GC-MS measurement conditions]
GC device: Agilent 5973N type quadrupole mass spectrometer Column: Agilent HP-5MS 0.25 mm id * 30 m, df = 0.25 μm
Column oven temperature: held at 40 ° C for 10 minutes, heated at 10 ° C / minute, held at 300 ° C for 15 minutes, inlet temperature: 290 ° C, interface temperature: 290 ° C
Injection method: Split (50: 1) Injection volume: 0.1 μL
Column flow rate: 0.7 mL / min (helium)
[GC-FID measurement conditions]
GC equipment: Hewlett Packard 6890 type FID detector GC
Column: Spelco PTE-5 0.25mm id * 30m, df = 0.25μm
Column oven temperature: held at 40 ° C. for 10 minutes, heated at 10 ° C./minute, held at 300 ° C. for 15 minutes, inlet temperature: 290 ° C.,
Interface temperature: 300 ° C
Injection method: Split (50: 1) Injection volume: 0.5 μl
Column flow rate: 0.7 mL / min (helium)
FID detector: hydrogen 40mL, air 450mL, makeup helium and carrier 45mL

[Silver plate corrosion test]
JIS K2513 “Petroleum products-Copper plate corrosion test method: Corresponding (ASTM D130)” cylinder method (jet fuel), instead of copper plate, JIS K2276 “Petroleum product-aviation fuel oil test method” “14. Silver plate corrosion test” The silver plate used in “Method” was used for evaluation. The test temperature is 50 ° C. and the test time is 3 hours.

[Rust prevention performance test]
Into a glass container, introduce 300 mL of sample and 30 mL of purified water to make a mixed solution, immerse a steel round bar test piece (steel plate), stir the mixed solution at 40 ° C. for 4 hours at 1000 rpm, and then the degree of corrosion of the test piece Evaluated. The steel round bar test piece used for the test is a carbon steel material of SGD 3M 13φ × 68 mm of JIS G3108 defined in JIS K2510. Table 6 shows the criteria for evaluating the degree of corrosion.

[Acceleration performance test]
An acceleration performance test was carried out by using a test dynamo apparatus having a displacement of 1500 cc and a fuel supply system of MPI using the gasoline of Examples 1 to 5 and Comparative Examples 1 and 2. In the test, after the vehicle was kept in a cold machine (25 ° C.) state, when the accelerator opening was accelerated up to 50% by the automatic driving device (Horiba Seisakusho, ADS7000), the initial speed was 0 to 50 ( km / hour) until the vehicle speed was reached. The results were compared with respect to the difference in acceleration time relative to the arrival time when Example 2 was used (acceleration time reduction rate). The result is combined with Tables 4-5, and is shown. The acceleration time reduction rate of the test gasoline was obtained from the following equation.
Acceleration time reduction rate (%) = (arrival time of Example 2−arrival time of test gasoline) ÷ (arrival time of Example 2) × 100

From Table 1, the high-purity ETBE base material has a reduced content of hydrocarbon compounds having no more than 4 carbon atoms and does not contain oxygen, and has a reduced vapor pressure and oxygen content, compared to the raw material US Chevron Chemical ETBE. It can be seen that the content of the hydrocarbon compound having 8 or more carbon atoms is decreased and the end point of the distillation property is decreased. Moreover, the antirust performance is improving by adding the detergent containing a antirust agent to this high purity ETBE.
From Table 4 and Table 5, Comparative Example 1 has good rust prevention performance as in Examples 1 and 2, but because the drivability index A is large, the acceleration rate increase rate is large and the drivability during cold operation is deteriorated. is doing. In Comparative Example 2, since the drivability index A is small, the acceleration time increase rate is small, and the cold drivability is good, but the content of aromatic hydrocarbons with 7 carbon atoms is large, and the aromatic carbonization with 9 carbon atoms. Since the ratio of the C7 aromatic hydrocarbon content to the hydrogen content is high, the rust prevention test (especially steel plate) is deteriorated. Moreover, in Example 3-5, both the operativity at the time of a cold machine and a rust prevention test are favorable.

Claims (7)

The ethyl tertiary butyl ether content is 1 to 20% by volume, the C7 aromatic hydrocarbon content is 3.0% by volume or less, and the (C9 aromatic hydrocarbon content) / (carbon Ethyl tertiary butyl ether-containing gasoline composition characterized in that the aromatic hydrocarbon content (number 7) ratio (capacity ratio) of Formula 7 is 3 or more, and the operability index A represented by the following formula is 1020 or less: object,
A = 5 × (T10) + 6 × (T50) + (T70) + 30 × (OX)
(Here, T10 represents 10% distillation temperature (° C.), T50 represents 50% distillation temperature (° C.), T70 represents 70% distillation temperature (° C.), and OX represents oxygen content (mass%).)   The sulfur content is 10 mass ppm or less, the (ethanol content) / (ethyl tertiary butyl ether content) ratio (volume ratio) is 0.001 to 0.010, and the research octane number is 91 to 98. Item 2. An ethyl tertiary butyl ether-containing gasoline composition according to Item 1. The ethyl tertiary butyl ether-containing gasoline composition according to claim 1 or 2, wherein a (tertiary butyl alcohol content) / (ethyl tertiary butyl ether content) ratio (volume ratio) is 0.004 to 0.010.   The ethyl tertiary butyl ether-containing gasoline composition according to any one of claims 1 to 3, comprising a rust inhibitor.   (N-heptane content + n-octane content) / (n-nonane content + n-decane content) ratio (volume ratio) obtained from catalytically cracked gasoline is 3 or less, and (n-heptane content) Any one of claims 1 to 4, comprising 50 to 80% by volume of a catalytically cracked gasoline base material having a (n-octane content) / (n-pentane content + n-hexane content) ratio (volume ratio) of 0.5 or less. A gasoline composition containing ethyl tertiary butyl ether according to claim 1.   It is a manufacturing method of the ethyl tertiary butyl ether containing gasoline composition in any one of Claims 1-5, Comprising: Manufacture of the ethyl tertiary butyl ether containing gasoline composition which mix | blends a hydrocarbon base material and an ethyl tertiary butyl ether base material Method. Ethyl tertiary butyl ether having a purity of 90 to 98% by volume is distilled and separated to obtain high purity ethyl tertiary butyl ether having a purity of 99% by volume or more and low purity ethyl tertiary butyl ether having a purity of less than 98% by volume. The method for producing an ethyl tertiary butyl ether-containing gasoline composition according to claim 6, wherein the tertiary butyl ether is used as an ethyl tertiary butyl ether base.