JP2006233033A - Gasoline composition exhausting small amount of carbon dioxide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gasoline composition having a remarkably decreased environmental load with a reduced amount of sulfur dioxide and carbon dioxide generated during combustion while securing sufficient driving properties. <P>SOLUTION: The gasoline composition has a research octane number of at least 93, preferably at least 95, a sulfur content of at most 10 mass ppm, preferably at most 1 mass ppm, a silver plate corrosion rating of at most 1, vapor pressure of at most 72 kPa, a 50 vol% distillation temperature of 100°C or lower as a distillation property, and a generated amount of carbon dioxide per calorific value of at most 0.284 g/kcal. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a low carbon dioxide emission gasoline composition that ensures environmental performance while ensuring sufficient operating characteristics.

  In recent years, as the scale of industrial economic activity expands globally, environmental destruction at the global level has become an important issue, and countermeasures for this are beginning to be studied worldwide. Above all, the global warming problem is concerned not only for human beings but also the earth itself, and it is a countermeasure to prevent the emission of carbon dioxide, which is the main cause of global warming, to the atmosphere. There is a strong demand for the establishment of measures. The Kyoto Protocol entered into force in February 2005, and Japan is obliged to reduce it by 6% compared to the 1990 level.

  Considering the aspect of automobile fuel, the demand for high-performance gasoline having high driving performance is increasing as the performance of automobiles increases. In particular, a report with a higher research octane number (RON) improves the driving performance of automobiles, improves energy conversion efficiency, and reduces carbon dioxide emissions, which is considered one of the global warming gases. There is. On the other hand, environmental pollution due to automobile fuel itself and its combustion exhaust gas has become a social problem, and an automobile fuel that maintains high driving performance and has a low environmental load is desired. In particular, from the viewpoint of exhaust gas purification, further reduction of the sulfur content is also desired. Further, gasoline for automobile fuel is almost composed of carbon and hydrogen, and when they are burned, carbon and hydrogen are converted into carbon dioxide and water, respectively, and at the same time, the generated heat is the power. Therefore, when the hydrocarbon compound burns, the lower the ratio of carbon contained in the fuel, the less carbon dioxide that is generated. Therefore, gasoline with a greater amount of hydrogen relative to carbon can suppress the global warming effect. It can be said that. In particular, the calorific value generated during combustion correlates with fuel efficiency, which is an indicator of the mileage of automobiles, and the amount of carbon dioxide generated per calorific value will be an important measure for environmental conservation on a global scale in the future. Become.

JIS K 2202 stipulates No. 1 automobile gasoline with an octane number of 96.0 or more and No. 2 automobile gasoline with 89.0 or more. The former is marketed as high-performance premium gasoline and the latter as regular gasoline. Yes. Conventionally, premium gasoline is mainly based on base materials having an octane number of 100 or more, such as catalytic reformed gasoline base materials, alkylate gasoline base materials, base materials having an octane number of 93 or higher, such as a light portion of catalytic cracked gasoline, Manufactured by blending various base materials. On the other hand, regular gasoline is produced by blending low-octane desulfurized straight-run naphtha, aroma fraction, and the like with a catalytic cracking gasoline base material as the center.

In general, cracked naphtha fractions such as catalytically cracked gasoline and various cracked gasolines contain olefins and aromatics, greatly contributing to the improvement of octane number. On the other hand, paraffins having a relatively low octane number are not preferred as a gasoline base material and have been reduced.
On the other hand, aromatic compounds and olefin compounds that are widely used as compounds having a high octane number are unlikely to be used in the future in terms of the environment. Specifically, aromatic compounds are said to be carcinogenic and have problems with the PRTR method, and partly change to particulate compounds (PM) when used as fuel for automobiles. Since the component is photochemically unstable and has a problem in storage stability, it has been pointed out that a solid compound such as a sludge is precipitated.

  Furthermore, although the aroma compound has an advantage of a high octane number, it has a high boiling point and cannot be contained so much in the gasoline base material from the viewpoint of distillation properties. In addition, as for the olefin component, the component having relatively low molecular weight tends to have a high vapor pressure although it has a high octane number, and it cannot be used in many gasoline base materials. There is a tendency to require a light distillation property, that is, a property having a relatively low boiling point and a low Reed vapor pressure (RVP).

  Taking the above situation into consideration and looking at the actual situation of gasoline production, cracked gasoline base materials produced by cracking heavy petroleum fractions are more economical to manufacture than other gasoline base materials. While it has the advantage of being able to do so, it contains a lot of sulfur. As a result, most of the sulfur content in the gasoline produced as described above is derived from the cracked gasoline base material. The sulfur content contained in the cracked gasoline base material can be easily reduced using a known technique of hydrotreating in the presence of high-pressure hydrogen and a catalyst. However, in that case, a large amount of the catalytic cracking gasoline base material is contained, and the olefin component having a high octane number is hydrogenated to lower the octane number of the base material. There was a problem that it was difficult to obtain gasoline. Recently, a technique for suppressing hydrogenation of the olefin and suppressing a decrease in octane number has been developed (see Patent Document 1), but the above-described problem that the olefin has an adverse effect on the environment has not been solved. In addition, development of paraffinic gasoline with a sulfur content reduced to 50 ppm by mass has been reported (see Patent Document 2), but it is necessary to reduce it to 10 ppm by mass considering future sulfur-free, At this sulfur level, there was no method for producing paraffinic gasoline having appropriate distillation properties and vapor pressure and having a high octane number.

  On the other hand, a technique is known that can improve the octane number, which is important as a gasoline base material, by skeletal isomerization of hydrocarbon oil under specific conditions. Isoparaffins produced by the skeletal isomerization reaction are effective as environmentally friendly clean fuels because they have little adverse effects on the environment, such as aromatic compounds and olefin compounds. Specifically, the skeletal isomerization reaction is generally a method of converting linear paraffin having a low octane number into a branched paraffin having a high octane number. In addition to a naphtha fraction derived from crude oil as its feedstock, FT (Fischer Tropsch) wax obtained by GTL (Gas To Liquid) technology using hydrogen or carbon monoxide generated from biomass, natural gas, steelworks, etc. as a raw material can be used.

As in the isomerization reaction, there is an alkylation reaction as a process capable of selectively producing isoparaffin. The alkylation reaction is a reaction in which an acid catalyst such as sulfuric acid is used to react mainly with a compound having 4 carbon atoms to produce an isoparaffin having 8 carbon atoms, and many apparatuses are already operating all over the world. (Refer nonpatent literature 1). However, because of the characteristics of the reaction, the product is mainly an isoparaffin having 8 carbon atoms, so that a multibranched isoparaffin having 8 carbon atoms can be obtained, but a multibranched isoparaffin having less than 8 carbon atoms is obtained. That was difficult. Since alkylate gasoline is composed of high-boiling components, it has been difficult to produce in large quantities in the past because of restrictions on distillation properties and because relatively expensive compounds with 4 carbon atoms are used as raw materials. .
Due to the circumstances as described above, the carbon dioxide per calorific value necessary for ensuring a sufficient practical performance and effectively suppressing the emission of carbon dioxide, while the sulfur content is still as low as 10 ppm by mass or less. No gasoline composition having a generation amount of 0.284 g / kcal or less has been proposed, and the production method has not been established.
JP 2003-183676 A International Publication No. 2002/046334 Edited by Petroleum Society, “Petroleum Refining Process”, p209 ～ 216, Kodansha Scientific, 1998

    The present invention has been made to solve the above problems, and the object of the present invention is to significantly reduce the load on the environment by reducing the amount of sulfur dioxide and carbon dioxide generated during combustion while ensuring sufficient operating characteristics. It is to provide a reduced gasoline composition.

The gasoline composition of the present invention has a research octane number of 93 or more, preferably 95 or more, a sulfur content of 10 mass ppm or less, a silver plate corrosion of 1 or less, a vapor pressure of 72 kPa or less, and a distillation property of 50% by volume distillation temperature. Is 100 ° C. or less, and the amount of carbon dioxide generated per calorific value is 0.284 g / kcal or less.
The gasoline composition of the present invention preferably has a carbon dioxide emission per volume of 2.34 kg / L or less, a sulfur content of 1 mass ppm or less, and a vapor pressure of 65 kPa or less. preferable.
In the gasoline composition of the present invention, the aromatic content / olefin content is 2.3 or less in volume ratio, further, the olefin content is 5 to 25% by volume, the aromatic content is 10 to 30% by volume, and further The hydrogen / carbon ratio is preferably 1.94 mol / mol or more.
Furthermore, the gasoline composition of the present invention preferably contains 1 to 15% by volume of an oxygen-containing compound, particularly ethyl tertiary butyl ether based on the total gasoline composition.
Still further, the gasoline composition of the present invention has a desulfurization catalytic cracking gasoline of 50% by volume or more based on the total gasoline composition and / or an isomerized gasoline of 1% by volume or more and 50% by volume or less based on the total gasoline composition. What is contained is preferable.
The gasoline composition of the present invention is preferably used as a gasoline engine fuel or a fuel cell fuel.

  The fuel composition of the present invention can ensure sufficient driving characteristics, particularly high fuel efficiency, and greatly reduce the amount of sulfur oxides discharged to the environment, carbon dioxide and hydrocarbons, thereby reducing the burden on the environment. There is a special effect that you can.

The gasoline composition of the present invention has a research octane number (RON) of 93 or more from the viewpoint of effectively improving fuel efficiency, preferably 95 or more,
95 to 110 are more preferable, and 95 to 105 are particularly preferable. This RON is measured by a method defined in JIS K 2280.

The sulfur content is preferably as low as possible from the viewpoint of reducing environmental burden, and is 10 mass ppm or less, preferably 5 mass ppm or less, more preferably 1 mass ppm or less, but considering the desulfurization cost It is preferable to set it to 0.1 mass ppm or more. This sulfur content is measured by the method defined in JIS K2541.
In addition, in order to prevent the trouble of the fuel center gauge of the vehicle due to a trace amount of active sulfur, the silver plate corrosion is preferably 1 or less, particularly 0. This silver plate corrosion is measured by the method prescribed in British Petroleum Institute Standard IP-227.

  The vapor pressure is set at 72 kPa or less, preferably 65 kPa or less as the vapor pressure at 37.8 ° C., from the viewpoint of preventing deficiencies in operability due to low temperature startability, vapor lock, etc., and particularly in summer, 44 to 65 kPa. Furthermore, it is preferable to set it as 44-60 kPa. This vapor pressure is measured by a method defined in JIS K 2258.

  The distillation volume of 50% by volume distillation temperature is preferably 100 ° C. or less, more preferably 80 to 95 ° C., from the viewpoint of reducing exhaust gas and improving acceleration. The 50 vol% distillation temperature of this distillation property is measured by the method specified in JIS K 2254.

In the fuel composition of the present invention, in particular, the amount of carbon dioxide generated per calorific value is 0.284 g / kcal or less, and when used as a fuel in this way, the amount of carbon dioxide emitted Can be reduced. The amount of carbon dioxide generated per calorific value is measured by calorific value (kcal / g) of gasoline measured by the calorific value test method of JIS K 2279 and the estimation method by calculation and ASTM D5291-96 (hydrocarbon combustion method). It is calculated from the carbon concentration (g / g) in gasoline that is completely burned and converted into carbon dioxide.
In order to easily reduce the amount of carbon dioxide generated per calorific value, 50% by volume or more of desulfurized catalytic cracking gasoline is contained based on the total gasoline composition, or 1 to 50% by volume of isomerized gasoline is contained. And good.

The above desulfurized catalytic cracking gasoline is used to produce petroleum fractions from light oil to reduced pressure light oil, degasified light oil obtained from heavy oil indirect desulfurization equipment, direct desulfurized oil obtained from heavy oil direct desulfurization equipment, atmospheric residual oil, etc. Obtained by desulfurization treatment of naphtha fraction (boiling point: 30 to 200 ° C., hereinafter referred to as “catalytic cracked naphtha fraction”) of catalytic cracked oil obtained by catalytic cracking using a catalyst such as silica alumina or zeolite. Is.
Examples of the catalytic cracking method for obtaining the catalytic cracking naphtha fraction include fluid catalytic cracking methods such as UOP catalytic cracking method, flexi cracking method, ultra-orthoflow method, Texaco fluid catalytic cracking method, RCC method, and HOC method. The residual fluid fluid catalytic cracking method can be given (Petroleum Society edition, “Petroleum refining process”, p125-156, Kodansha Scientific issue (1998)). This catalytic cracked naphtha fraction contains a high octane gasoline component.

As the desulfurization catalytic cracking naphtha fraction, the desulfurization treatment method used in ordinary petroleum refining can be used as the desulfurization catalytic cracking naphtha fraction. In particular, the desulfurization treatment can be performed while suppressing the decrease in octane number. It is preferable to use a detachable and removable sulfur method. This sorption / removal sulfur method is not particularly limited as long as it has a sorption function for sulfur compounds. A porous desulfurization agent containing at least one selected from copper, zinc, nickel and iron is preferably used. A preferred desulfurizing agent contains 0.5 to 85% by mass, particularly 1 to 80% by mass of a metal component such as copper. The production method of the desulfurization agent is not particularly limited, but a production method in which a porous carrier such as alumina is impregnated with metal components such as copper, supported, and fired, or a metal component such as copper and a component such as aluminum by a coprecipitation method A preferable method is a production method in which the above is precipitated and subjected to steps such as molding and baking. Alternatively, the molded and fired desulfurizing agent may be further impregnated and supported with a metal component and fired. The desulfurization agent may be used as it is, or may be used after being treated in a hydrogen atmosphere. The specific surface area of the desulfurizing agent is preferably 30 m ² / g or more, particularly 50 to 600 m ² / g. The composition and production method of the desulfurizing agent are not particularly limited, but preferred examples include desulfurizing agents as disclosed in Japanese Patent No. 3324746, Japanese Patent No. 3230864 and Japanese Patent Laid-Open No. 11-61154.
In this case, the desulfurization temperature can be selected from a range of 0 to 400 ° C., preferably 20 to 380 ° C., and LHSV is preferably selected from a range of 0.01 to 10,000 h ⁻¹ .
In order to promote desulfurization of thiophenes that are not easily desulfurized only by contacting with a desulfurizing agent, desulfurization treatment may be performed in the presence of hydrogen. However, in this case, the hydrogen partial pressure is preferably less than 1 MPa, and more preferably less than 0.6 MPa, in order to avoid hydrogenation of the olefin and a decrease in the octane number of the resulting gasoline base.

On the other hand, isomerized gasoline is obtained by isomerizing a desulfurized straight naphtha fraction and / or a wax obtained by the Fischer-Tropsch method.
This isomerization treatment method is not particularly limited, but is generally used as a catalyst under a hydrogen atmosphere, "platinum chlorinated alumina" with platinum supported on chlorinated alumina, "platinum zeolite" with platinum supported on zeolite In addition, solids represented by “platinum sulfate zirconia” supporting platinum on a carrier containing zirconia and sulfuric acid, and “platinum tungstate zirconia” supporting platinum on a carrier containing an oxide component of zirconia and tungsten, etc. A method using an acid catalyst or the like is preferable.
The isomerization reaction conditions vary depending on the catalyst used, but in general, the reaction temperature is 120 to 250 ° C., the reaction pressure is 0.5 to 5 MPa, and the liquid space velocity (LHSV) is 0.5 to 5 h ⁻¹ . A part of the naphthene is opened, and at the same time, normal paraffin is isomerized to increase isoparaffin. A particularly preferred isomerization method is a method in which a platinum tungstate zirconia catalyst is used and the reaction temperature is 180 to 220 ° C., the reaction pressure is 0.5 to 3.5 MPa, and the LHSV is 1.5 to 3 h ⁻¹ . In this case, it is preferable to increase the yield by a method in which a heavy component, a non-reacted component, a low octane product, etc. of the reaction product oil are recycled and reacted again.

  In the gasoline composition of the present invention, in order to more easily achieve the carbon dioxide generation amount per calorific value of 0.284 g / kcal or less, the carbon dioxide emission amount per volume is preferably 2.34 kg / L. Hereinafter, it is more preferably 2.0 to 2.34 kg / L. This carbon dioxide emission per volume is calculated from the carbon concentration in gasoline as measured by ASTM D5291-96 (hydrocarbon combustion method), assuming that the entire amount is converted to carbon dioxide by complete combustion. is there.

  For the same reason, the hydrogen / carbon ratio is preferably 1.94 mol / mol or more, more preferably 1.94 to 2.4 mol / mol. This hydrogen / carbon ratio is calculated from the contents of carbon and hydrogen measured by ASTM D5291-96 (hydrocarbon combustion method).

  Furthermore, for the same reason, the aromatic content / olefin content is preferably 2.3 or less, more preferably 1.0 to 2.3 in volume ratio, and the olefin content is preferably 5 to 25. The volume%, more preferably 10 to 20 volume%, and the aromatic content is preferably 10 to 30 volume% or less, more preferably 20 to 30 volume%. The olefin content and aromatic content are measured by a method defined in JIS K 2536 (fluorescent indicator adsorption method).

  When the gasoline composition of the present invention contains an oxygen-containing compound, it is easier to adjust the RON to 93 or more, or the carbon dioxide generation amount per calorific value to 0.284 g / kcal or less.

  As this oxygen-containing compound, for example, alcohols having 2 to 5 carbon atoms and ethers having 4 to 8 carbon atoms are suitable, and specifically, from alcohols such as methanol, ethanol, propyl alcohol, and alcohols. Derivatives of ethers and esters such as ethyl isopropyl ether, ethyl tertiary butyl ether (ETBE), ethyl secondary butyl ether (ESBE), diisopropyl ether, tertiary amyl ethyl ether (TAEE), ethyl acetate, ethyl propionate In particular, it is preferable to use ethyl tertiary butyl ether. These oxygenated compounds are used in an amount of 1 to 15% by volume, preferably 3 to 12% by volume, more preferably 5 to 10% by volume, based on the total gasoline composition. If the amount is too small, the effect of addition is small. If the amount is too large, impurities such as moisture are accompanied, which may cause troubles such as corrosion of pipes and sealing materials. For example, since ethanol dissolves water indefinitely, if it is contained too much in the fuel, water may be concentrated and accumulated in the automobile engine, which may have an adverse effect. Furthermore, when there are many oxygenated compounds in the fuel oil, for example, if the amount exceeds 15% by volume, it will deviate from the optimum value of the air / fuel ratio of the existing engine. There is a drawback that the amount of nitrogen oxide (NOx) increases. Further, since oxygen-containing compounds generally have a lower calorific value than other gasoline base materials and may reduce fuel consumption, it is not preferable to use too much.

The gasoline composition according to the present invention includes, in addition to oxygenated compounds, desulfurized catalytic cracking gasoline fraction, and isomerized gasoline, catalytic cracking gasoline fraction, catalytic reformed gasoline fraction, alcohol, which are widely used as ordinary gasoline base materials. It can be prepared by appropriately blending chelate gasoline, desulfurized straight-run gasoline fraction and the like. In preparing this gasoline composition, RON, sulfur content, vapor pressure, distillation properties, silver plate corrosion, carbon dioxide generation amount per calorific value, etc. of the above various gasoline base materials are measured or calculated in advance. It can manufacture comparatively easily by mix | blending various base materials so that it may become the said specific range.
Preferred blending amounts are 0 to 50% by volume of isomerized gasoline, 45 to 80% by volume of desulfurized catalytic cracking gasoline fraction, 5 to 25% by volume of catalytic reformed gasoline fraction, and 5 to 15 of alkylate gasoline. Volume%, ETBE is 0 to 15 volume%.

  As a preferable embodiment of the carbon dioxide low emission gasoline composition of the present invention, a known fuel additive can be blended if necessary. Although these compounding quantities can be selected suitably, it is usually preferable to set it as 0.1 mass% or less as a total amount of an additive. Examples of additives that can be used in the carbon dioxide low emission gasoline composition of the present invention include amine-based, phenol-based, aminophenol-based antioxidants, Schiff-type compounds, thioamide-type compounds, and other metal deactivators. , Surface ignition inhibitors such as organophosphorus compounds, detergent dispersants such as succinimides, polyalkylamines and polyetheramines, anti-icing agents such as polyhydric alcohols and their ethers, alkali metal salts and alkaline earths of organic acids Metal salts, auxiliary agents such as sulfates of higher alcohols, anionic surfactants, cationic surfactants, antistatic agents such as amphoteric surfactants, rust inhibitors such as alkenyl succinates, quinizarin, coumarins, etc. And a colorant such as an azo dye.

  Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to these examples.

  Gasoline base materials having the properties shown in Table 1 were blended at the blending ratios shown in Tables 2, 3 and 4 to prepare gasoline compositions as Examples and Comparative Examples. The gasoline base used was prepared as follows.

Isopentane (iC5)
The naphtha fraction was obtained by precision distillation after hydrodesulfurization.

Desulfurization straight naphtha fraction (DSLG)
It was obtained by hydrodesulfurizing a naphtha fraction of Middle Eastern crude oil and distilling off the light fraction.

Alkylate gasoline (ALKG)
A fraction containing butylene as a main component and a fraction containing isobutane as a main component were reacted with a sulfuric acid catalyst to obtain a hydrocarbon having a high isoparaffin content.

Reformed gasoline (AC9)
Desulfurized heavy naphtha is reacted with a solid reforming catalyst using a moving bed reactor to reform to a hydrocarbon with a high aroma content to obtain reformed gasoline. The reformed gasoline can be used as it is, but here, a fraction (AC9) containing 80% or more of hydrocarbons having 9 carbon atoms was obtained by distillation separation.

Desulfurization catalytic cracking naphtha fraction (FCCG)
Hydrocarbons with high olefin content were obtained by cracking desulfurized light oil or desulfurized heavy oil with a solid catalyst using a fluidized bed reactor. Furthermore, hydrocarbons having a low sulfur content were obtained by collecting and removing FCCG. After sulfiding a catalyst with 20% by mass of nickel supported on alumina, a vacuum gas oil of Middle Eastern crude oil under the conditions of reaction temperature 250 ° C., reaction pressure normal pressure, LHSV4h ⁻¹ , H ₂ / oil ratio 340 NL / L Diene reduction treatment is performed by passing through a catalytic cracked naphtha fraction obtained by fluid catalytic cracking using a hydrorefined fraction as the main feedstock. Then, the reduction process of the copper zinc aluminum complex oxide (copper content 35 mass%, zinc content 35 mass%, aluminum content 5 mass%) prepared by the coprecipitation method was performed. The diene-treated catalytically cracked gasoline was then sorbed for 20 hours under conditions of a reaction temperature of 100 ° C., a reaction pressure of normal pressure, LHSV of 2.0 h ⁻¹ , and an H ₂ / oil ratio of 0.06 NL / L. A desulfurized catalytic cracking naphtha fraction (FCCG) desulfurized with a functional desulfurizing agent was obtained.

Isomerized gasoline (ISO)
The desulfurized straight naphtha fraction (DSLG) was obtained by reacting with a solid acid catalyst in the presence of hydrogen. As the catalyst, a catalyst in which 0.5% by mass of platinum was supported on zirconia sulfate was used after reduction treatment. The proportion of zirconia in the catalyst was 43.5% by mass as zirconium element, the proportion of alumina was 16.1% by mass as aluminum element, and the proportion of sulfur was 2.9% by mass as element. The reaction was carried out under the conditions of a reaction temperature of 200 ° C., a hydrogen pressure of 1.0 MPa, an LHSV of 1.5 h ⁻¹ , an H ₂ / oil ratio of 5.0 mol / mol to obtain isomerized gasoline (ISO).

Ethyl tertiary butyl ether (ETBE)
Commercially available ethyl tertiary butyl ether was used.

In addition, the property of the gasoline base material and the prepared gasoline composition was measured by the following method.
The density was measured by the density test method of JIS K 2249, the vapor pressure of the Reed method was measured by the vapor pressure test method (Reed method) of JIS K 2258, and the distillation property was measured by the atmospheric pressure distillation test method of JIS K 2254. The sulfur content was measured by the sulfur content test method of JIS K2541. The total calorific value was measured by a calorific value test method of JIS K 2279 and a calculation estimation method. The total calorific value (Hg: higher calorific value) and the true calorific value (Hn: lower calorific value) can be converted by the following equation according to JIS K 2279.
Hn = Hg-6 (9h + W)
Where Hn: True calorific value (cal / g)
Hg: Total calorific value (cal / g)
h: Hydrogen content (mass%)
W: Moisture (% by mass)

  In Example 1 and Example 2, the gasoline base material was blended at the mixing ratio shown in Table 2 to produce the gasoline composition of the present invention. The gasoline compositions of Example 1 and Example 2 are high in RON and preferable in distillation properties by adopting isomerized gasoline as compared with the conventional gasolines in Comparative Examples 1 and 2. It can be seen that the amount of carbon dioxide emission per fuel is small and the amount of carbon dioxide generated per calorific value is reduced. As a result, the gasoline compositions of Example 1 and Example 2 have preferable distillation properties, high octane number, and low CO 2 even though the vapor pressure and sulfur concentration are similar to those of Comparative Example 1 and Comparative Example 2. It can be seen that the carbon dioxide low emission gasoline has excellent practical performance capable of reducing the amount of carbon generated.

Further, a gasoline composition was prepared by blending the gasoline base at the mixing ratio shown in Table 3. In Example 3, the gasoline composition of the present invention was prepared by containing ETBE. As a result, by containing an oxygen-containing compound, the amount of carbon dioxide emitted per fuel can be reduced, and the amount of carbon dioxide generated per calorific value is reduced. Compared with the gasoline composition of the present invention of Example 3, the conventional gasolines of Comparative Example 3 and Comparative Example 4 do not use isomerized gasoline, so the octane number tends to be low. A lot of AC9 and isopentane were used. However, it can be seen that the ratio of aromatics with a large amount of carbon dioxide emission becomes high, the amount of carbon dioxide emission per fuel is large, and the amount of carbon dioxide generation per calorific value is increasing.
In Comparative Example 5 shown in Table 3, although ETBE is contained, the FCCG content is low and isomerized gasoline is not included. Therefore, in order to improve the octane number, a large amount of AC9 containing a large amount of aromatics should be used. Inevitably, carbon dioxide emissions are increasing. It shows that it is not enough to contain ETBE.

A gasoline composition containing ETBE at the mixing ratio shown in Table 4 was prepared. The gasoline compositions of the invention of Examples 4 to 6 contain 50% or more by volume of FCCG, contain isomerized gasoline, or both so that they have an octane number greater than 95 and are suitable. It can be seen that a carbon dioxide low emission gasoline composition having distillation properties and vapor pressure and having excellent practical performance capable of reducing the amount of carbon dioxide generated can be obtained. In contrast, in Comparative Example 6 and Comparative Example 7, the gasoline composition was prepared so as to contain a large amount of ETBE, but although there was an advantage that the octane number was high, the fuel oil contained a large amount of oxygen, the hydrogen / carbon ratio was low. In addition, since the calorific value is low, the amount of carbon dioxide generated per calorific value is increased. Therefore, it indicates that using too much ETBE is not always a good measure.

As described above, the gasoline compositions of the present invention of Examples 1 to 6 have a high octane number and olefins even when the vapor pressure, distillation properties, and sulfur concentration are similar to those of the comparative example. Since the ratio of the aromatic component to the component is low, it can be seen that the gasoline composition has a low carbon dioxide emission and has excellent practical performance capable of reducing the amount of carbon dioxide generated.

  Since the gasoline composition of the present invention has a high content of branched saturated hydrocarbon compounds, it can be used not only as a fuel for gasoline engines but also as a fuel for fuel cells. Since it has, it is suitable and can also be used as a gasoline common to a gasoline engine and a fuel cell.

Claims (13)

  Research method Octane number is 93 or more, sulfur content is 10 mass ppm or less, silver plate corrosion is 1 or less, vapor pressure is 72 kPa or less, distillation volume of 50 vol% distillation temperature is 100 ° C or less, carbon dioxide generation per calorific value A gasoline composition having a 0.284 g / kcal or less.   The gasoline composition according to claim 1, wherein the research octane number is 95 or more.   The gasoline composition according to claim 1 or 2, wherein the carbon dioxide emission per volume is 2.34 kg / L or less.   The gasoline composition according to any one of claims 1 to 3, wherein a sulfur content is 1 mass ppm or less.   The gasoline composition according to any one of claims 1 to 4, wherein the vapor pressure is 65 kPa or less.   6. The gasoline composition according to claim 1, wherein the hydrogen / carbon ratio is 1.94 mol / mol or more.   The gasoline composition according to any one of claims 1 to 6, wherein the aromatic content / olefin content is 2.3 or less in volume ratio.   The gasoline composition according to any one of claims 1 to 7, wherein the olefin content is 5 to 25% by volume and the aromatic content is 10 to 30% by volume.   The gasoline composition according to claim 1, comprising an oxygen-containing compound.   The gasoline composition according to claim 9, wherein the oxygen-containing compound is ethyl tertiary butyl ether, and the content thereof is 1 to 15% by volume based on the total gasoline composition.   The gasoline composition according to any one of claims 1 to 10, wherein the desulfurized catalytically cracked gasoline contains 50% by volume or more based on the total gasoline composition.   The gasoline composition according to any one of claims 1 to 11, wherein isomerized gasoline is contained in an amount of 1 to 50% by volume based on the total gasoline composition.   The gasoline composition according to any one of claims 1 to 12, which is used as a fuel for a gasoline engine or a fuel for a fuel cell.