KR101579654B1 - Aviation gasoline composition - Google Patents

Abstract

The present invention relates to a composition comprising 75 to 95% by volume of a hard alkylate; And 5% to 25% by volume of mixed C5 oil containing linear C5 paraffins and C5 olefins.

Description

AVIATION GASOLINE COMPOSITION [0002]

The present invention relates to aviation gasoline compositions.

Gasoline, the most widely known petroleum product, refers to boiling liquids in the 30 to 200 ° C range when crude oil is fractionally distilled. Gasoline is also often called gasoline, which, as its name suggests, is easily vaporized at room temperature and flammable, and explosive when mixed with air.

Gasoline is widely used in automobile, aviation, and industrial fields. Most cars use gasoline as fuel, and aviation gasoline is used as fuel for light aircraft with propellers. Industrial gasoline is used for dry cleaning, rubber industry, paint, and cleaning.

Especially, air gasoline is gasoline refined especially for aircraft gasoline engines, and generally has low distillation temperature, high octane number and low impurities.

Conventional air gasoline compositions use branched C5 paraffins such as iso-pentane as C5 oil. In addition, since aromatic compounds such as toluene are used in an air gasoline composition in an amount of about 5% by volume or more relative to the total air gasoline composition, these aromatic compounds are toxic substances, which are harmful to humans and the environment.

The present invention relates to a method for improving the safety and combustion performance of air gasoline and minimizing the amount of an aromatic compound used as a toxic substance in comparison with a conventional air gasoline composition using a large amount of an aromatic compound which is a toxic substance and a side chain type C5 paraffin, To 95% by volume; And 5% to 25% by volume of mixed C5 oil containing linear C5 paraffins and C5 olefins.

However, the technical problem to be solved by the present invention is not limited to the above-mentioned problems, and other matters not mentioned can be clearly understood by those skilled in the art from the following description.

The present invention relates to a composition comprising 75 to 95% by volume of a hard alkylate; And 5% to 25% by volume of mixed C5 oil containing linear C5 paraffins and C5 olefins.

From 0.1% by volume to 5% by volume of an aromatic compound.

And may further contain 0.01 ml / l to 0.53 ml / l of tetraethyl lead (TEL: tetra ethyl lead).

The boiling point of the hard-boiled alkylate may be below 170 캜.

The mixed C5 oil fraction may be pyrolysed naphtha cracking residues, hydrocracked naphtha cracked residues or fluidized catalytic cracking (FCC) cracked heavy oil cracking residues.

The volume ratio of the linear C5 paraffin and the C5 olefin may be from 15:85 to 95: 5.

The C5 olefin is preferably selected from the group consisting of 1-pentene, 2-pentene, 2-methyl-1-butene, 2-butene, 1,3-pentadiene, 1,4-pentadiene, 2,3-pentadiene, cyclopentene, cyclopentene, cyclopentadiene, and mixtures thereof. < / RTI >

The aromatic compound may be selected from the group consisting of benzene, toluene, xylene, ethylbenzene, aniline, toluidine, phenol, cresol, Lt; / RTI >

The motor octane number of the air gasoline composition may be 99.6 or higher.

The Reid Vapor Pressure (RVP) of the air gasoline composition may be 38.0 kPa to 49.0 kPa.

The performance number of the air gasoline composition may be 130.0 or higher.

The present invention relates to a composition comprising 75 to 95% by volume of a hard alkylate; And 5% to 25% by volume of a mixed C5 oil containing linear C5 paraffins and C5 olefins, wherein the safety and safety of air gasoline is improved by using mixed C5 oil containing linear C5 paraffins and C5 olefins. The combustion performance can be improved, and the amount of the aromatic compound used as the toxic substance can be minimized.

Figure 1 shows the relationship between the tetraethyl lead content (TEL: tetra ethyl lead) and the figure of merit.

The present inventors have been studying a substitute for the side chain type C5 paraffin used in an airgel gasoline composition, and have found that by using a mixed C5 oil containing linear C5 paraffins and C5 olefins, it is possible to produce air gasoline with improved safety and combustion performance And completed the present invention.

Hereinafter, the present invention will be described in detail.

The present invention relates to a composition comprising 75 to 95% by volume of a hard alkylate; And 5% to 25% by volume of mixed C5 oil containing linear C5 paraffins and C5 olefins.

The air gasoline composition according to the present invention may further comprise from 0.1% by volume to 5% by volume of an aromatic compound.

Also, the air gasoline composition according to the present invention may further contain 0.01 ml / l to 0.53 ml / l of tetraethyl lead (TEL).

The air gasoline composition according to the present invention preferably comprises from 75% by volume to 95% by volume of the hard alkylate, more preferably from 75% by volume to 85% by volume of the hard alkylate, but is not limited thereto. If the volume of the hard aluminate is less than the above range, the main combustion performance such as the anti-knocking performance or the calorific value of the air gasoline may be deteriorated. If the volume of the hard aluminate exceeds the above range There is a problem that the starting pressure failure or the abnormal combustion may be caused because the vapor pressure or the distillation property required by the aviation engine is not satisfied.

Alkylates are products of alkylation reaction, mainly high octane gasoline components synthesized by alkylation. Generally, butane oil containing isobutane as a main component and butylene, isobutylene or propylene are reacted with hydrogen fluoride or sulfuric acid as a catalyst. The main component is a branched paraffin mixture having various structures.

The general alkylate has a boiling point of about 185 ° C, and such an alkylate can not be used as an air gasoline composition, and thus the light gasoline composition according to the present invention uses a light alkylate.

The boiling point of the hard-boiling alkylate is preferably 170 ° C or lower, which can be prepared by distillation and re-distillation of the alkylate. If the boiling point of the hard alkylate exceeds 170 ° C, the oxidation stability of air gasoline may be degraded and incomplete combustion may be caused.

The air gasoline composition according to the present invention preferably contains 5 to 25 volume% of mixed C5 oil, more preferably 15 to 25 volume% of mixed C5 oil, but is not limited thereto. If the volume of the mixed C5 oil is less than the above range, the vapor pressure or the distillation property required by the aviation engine can not be satisfied, which may lead to poor starting performance or abnormal combustion. If the volume of the mixed C5 oil exceeds the above range There is a problem that the vapor pressure or the distillation property required by the aviation engine can not be met, thereby causing vapor lock or abnormal combustion.

C5 olefins present in nature are close to 0 vol%. However, the mixed C5 oil fraction according to the present invention contains a large amount of C5 olefin, and the mixed C5 oil fraction may be pyrolysed naphtha decomposed residual oil, hydrocracked naphtha decomposed residual oil, Catalytic cracking (FCC) cracked heavy oil decomposition residue may be unique. At this time, the mixed C5 oil fraction may be decomposed under a specific catalyst at a specific temperature and a specific pressure condition.

The naphtha cracked residue may be pyrolysed in the presence of a specific catalyst at a specific temperature and under specific pressure conditions, or may be prepared by pyrolysis followed by hydrogenation to prepare a mixed C5 oil containing linear C5 paraffins and C5 olefins. In addition, the naphtha-decomposed residual oil can be preliminarily removed from the naphtha-decomposed residual oil by pretreatment before pyrolysed, and the hetero compounds and metal components containing sulfur, nitrogen, oxygen and the like, which are contained in the residual naphtha residue, can be removed in advance.

It has also been found that naphtha can be obtained from naphtha cracked residues produced through hydrocracking in a BTX process that produces benzene, toluene and xylene by reforming the naphtha under specific catalysts at specific temperature and pressure conditions, A mixed C5 oil fraction containing paraffins and C5 olefins can be prepared. In addition, the naphtha-decomposed residual oil can be preliminarily removed from the naphtha-decomposed residual oil through hydrothermal decomposition before hydrocracked, such as sulfur compounds, nitrogen compounds, oxygen compounds, and the like. Thus, when hydrocracked naphtha cracked residues are used in the BTX process as a mixed C5 fraction, even if the mixed C5 fraction is used at less than 15% by volume, the vapor pressure or distillation property required by the air-fuel engine can be satisfied In addition, it is also possible to prepare a mixed C5 oil containing linear C5 paraffins and C5 olefins through fluidized catalytic cracking (FCC) in the presence of a specific catalyst at a specific temperature and under specific pressure conditions You may.

The mixed C5 oil fraction may contain, in addition to linear C5 paraffins and C5 olefins, not more than 75% by volume of C4-olefin, C6 + oil, side chain type C5 paraffin, and mixtures thereof. At this time, the C4-olefin, the C6 + oil, the side chain type C5 paraffin, and the mixture thereof may be impurities due to pyrolysis, hydrocracking or fluidized bed catalytic catalytic cracking, and impurities contained by intentional or unintentional random mixing Lt; / RTI >

The volume ratio of the linear C5 paraffin and the C5 olefin is preferably 15:85 to 95: 5, but is not limited thereto. When the volume ratio of the linear C5 paraffins and the C5 olefins is less than 15:85, the oxidation stability of the air gasoline may be lowered or the incomplete combustion may occur. If the volume ratio of the linear C5 paraffins and the C5 olefins exceeds 95: 5 There is a problem that the safety and combustion performance of air gasoline or the effect of minimizing the use amount of aromatic compounds, which are toxic substances, can not be significantly increased.

The linear C5 paraffin may be n-pentane.

The C5 olefin is preferably selected from the group consisting of 1-pentene, 2-pentene, 2-methyl-1-butene, 2-butene, 1,3-pentadiene, 1,4-pentadiene, 2,3-pentadiene, cyclopentene, cyclopentene, cyclopentadiene, and mixtures thereof. < / RTI >

In the conventional air-gasoline composition, side-chain type C5 paraffin such as iso-pentane is used as C5 oil. In the present invention, as a substitute for side chain type C5 paraffin, excellent flash point and high standard enthalpy of heat generation (kJ / The use of mixed C5 oil containing linear C5 paraffins and C5 olefins has the advantage of improving the safety and combustion performance of air gasoline compositions.

At this time, the linear C5 paraffin or C5 olefin has a higher flash point and a higher calorific value than the side chain type C5 paraffin, and the specific contrast is as shown in Table 1 below.

C5 oil flash point
(° C) Molar mass
(g / mol) density
(g / l) Standard exothermic enthalpy (kJ / mol) Conversion standard heating enthalpy (kJ / l) Conversion standard heat enthalpy comparison (%) Branched C5 paraffin iso-pentane -51 72.15 616 -3504.4 -29919.76 100.0 Linear C5 paraffin n-pentane -49 72.15 626 -3509.0 -30445.38 101.8 C5 olefin 1-pentene -51 70.13 641 -3349.7 -30616.82 102.3 cis-2-pentene -18 70.13 650 -3343.2 -30986.45 103.6 trans-2-pentene -18 70.13 649 -3338.7 -30897.14 103.3 2-methyl-1-butene -48 70.13 650 -3335.74 -30917.31 103.3 2-methyl-2-butene -20 70.13 662 -3328.6 -31420.69 105.0

As shown in Table 1, n-pentane, 1-pentene, and 2-methyl-1-butene maintain the same level of flash point as iso-pentane but have a high standard enthalpy of heat generation (kJ / l). cis-2-pentene, trans-2-pentene and 2-methyl-2-butene have a higher flash point than isopentane and have a higher standard enthalpy of heat generation (kJ / l).

That is, the linear C5 paraffin or C5 olefin maintains or is at an equivalent level of flash point to the side chain type C5 paraffin, and the standard exothermic enthalpy (kJ / l) is about 1.8% to about 5.0% higher.

In this case, the flash point means the lowest temperature which is ignited by the external flame when the increase caused by the heating of the fuel is mixed with the air. Generally, the flash point is a standard to measure the safety of kerosene and light oil. It is not measured in the case of conventional gasoline, but it is similar to the flash point level of C4 to C5 series fuel due to low air temperature at high altitude It is an important standard in the case of aviation gasoline. In this case, the lower the flash point, the higher the risk of an explosion by an external ignition source when a small amount of fuel leaks from the fuel tank in the aircraft. Since C5 oil in aerosol gasoline compositions has the lightest properties, the flash point of C5 oil is particularly important for safety.

In addition, the standard enthalpy of heat (kJ / l) means the calorific value per unit volume. As the calorific value increases, not only the combustion performance such as the fuel consumption and output of the fuel is improved but also the fatal accident Can be prevented.

The air gasoline composition according to the present invention preferably further comprises 0.1% by volume to 5% by volume of an aromatic compound, more preferably 0.1% by volume to 3% by volume, but is not limited thereto. In this case, when the aromatic compound further contains less than the above-mentioned volume range, there is a problem that the motor octane value of the air gasoline composition is not sufficiently increased, and the anti-knock performance of the air gasoline is deteriorated. There is a problem that it is detrimental to the human body and the environment due to the toxicity, the acute toxicity and the increase of the carcinogen.

In addition, since aromatic compounds cause incomplete combustion and generation of air engine sediments, safety and combustion performance can be improved by minimizing their use, and aromatic compounds are considerably more expensive than other components of air gasoline compositions, There is an advantage of contributing to the production cost reduction by minimizing the usage amount.

That is, the air gasoline composition according to the present invention is characterized in that safety and combustion performance are excellent even when the amount of aromatic compound, which is a toxic substance, is minimized.

The aromatic compound is a component for increasing the motor octane number of the air gasoline composition, while it is a harmful, acute toxic and carcinogenic substance and is a benzene, toluene, xylene, ethylbenzene, aniline, , Toluidine, phenol, cresol, and mixtures thereof.

The air gasoline composition according to the present invention preferably further contains 0.01 to 0.53 ml / l of tetraethyl lead (TEL: tetra ethyl lead), more preferably 0.43 to 0.53 ml / l But is not limited thereto. At this time, when the amount of tetraethyl lead further contains less than the above volume range, there is a problem that the anti-knocking performance of air gasoline is lowered because the motor octane value of the air gasoline composition is not sufficiently increased. If it contains more than the volume range, there is a problem that it is harmful to the human body and the environment like an aromatic compound.

The motor octane number of the air gasoline composition may be 99.6 or higher.

The Reid Vapor Pressure (RVP) of the air gasoline composition may be 38.0 kPa to 49.0 kPa. In this case, when the radiant vapor pressure of the air gasoline composition is less than 38.0 kPa, there is a problem that the aircraft is not started, and when the radiant vapor pressure of the air gasoline composition exceeds 49.0 kPa, the airgel composition is difficult to maintain the liquid phase.

The air gasoline composition maintains a motor octane number of at least 99.6 and maintains a Reid Vapor Pressure (RVP) of 38.0 kPa to 49.0 kPa to produce a gas grade ASTM D910 (Grade 100 / Grade 100LL / Grade 100VLL) and Def-Stan 91-90.

The performance number of the air gasoline composition may be 130.0 or higher. The performance index of an aviation gasoline composition is a value used for evaluating the anti-knock performance of aviation gasoline, which is determined to be proportional to the maximum output of the aviation engine, which is tetra ethyl lead (TEL) It tends to increase in proportion to the content.

At this time, the relationship between the tetraethyl lead content (TEL: tetra ethyl lead) and the figure of merit is shown in FIG.

Accordingly, the air gasoline composition according to the present invention can improve the safety and combustion performance of air gasoline and minimize the amount of aromatic compound used as a toxic substance by using mixed C5 oil containing linear C5 paraffin and C5 olefin.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited by the following examples.

[ Example ]

Example

A mixed C5 oil containing linear C5 paraffin and C5 olefin was prepared by supplying hydrotreated naphtha-decomposed residual oil after pyrolysis at Lotte Chemical Co., Ltd. Yeosu plant. 80 liters of a light alkylate having a boiling point of 123 ° C manufactured by GS Caltex Co., Ltd., 17 liters of a mixed C5 oil prepared, 3 liters of toluene and 0.40 ml / liter of tetraethyl lead (TEL) To produce an air gasoline composition. At this time, the prepared mixed C5 oil fraction was mixed with 4.0 liters of n-pentane and 1-pentene, cis-2-pentene, trans-2-pentene, Lt; RTI ID = 0.0 > C5 < / RTI >

Experimental Example

To confirm whether the air gasoline composition according to the embodiment meets the international standards ASTM D910 (Grade 100 / Grade 100LL / Grade 100VLL) and Def-Stan 91-90 of aviation gasoline, experiments as shown in Table 2 were performed.

Experiment Item Experimental Method International standard of aviation gasoline Experiment result Copper-strip, @ 100 ℃, 2 hours ASTM D130 Up to 1b 1a distillation 10%, EVA (占 폚) ASTM D86 Up to 75 68.5 Recovery, 40% (℃) Up to 75 97 50%, EVA (占 폚) Up to 105 101.3 90%, EVA (占 폚) Up to 135 110.7 EP (占 폚) Up to 170 124 EVA 10 + 50 (占 폚) At least 135 169.8 Recovery (% by volume) At least 97.0 97.5 Residue (vol%) Up to 1.5 1.0 Loss (% by volume) Up to 1.5 1.5 API Specific Gravity, @ 60 ° F ASTM D1298 - 69.5 Density, @ 15 ℃ (㎏ / ℓ) ASTM D1298 - 0.7037 Motor octane ASTM D2700 At least 99.6 100.9 Performance index ASTM D909 130.0 or higher 129.6 Tetraethyl Lead, ml TEL / L ASTM D5059 0.53 or less 0.40 Raid vapor pressure, @ 37.8 ° C (kPa) ASTM D5191 38.0 to 49.0 39.2 Sulfur (% by weight) ASTM D4294 Up to 0.05 0.001 Net calorific value (MJ / kg) ASTM D3338 At least 43.5 44.178 Freezing Point (℃) ASTM D2386 -58 max L-75 Moisture reactivity (ml) ASTM D1094 Up to ± 2 0.0 Oxidation stability (aged for 5 hours) ASTM D873 Up to 2 0 Electrical Conductivity (Ps / m) ASTM D2624 Up to 450 0

As shown in the above Table 2, the performance number of the air gasoline composition according to the embodiment was 129.6, which was slightly lower than the international standard (130.0 or higher) of the air gasoline. However, the tetraethyl lead content According to the proportional relationship of the figure of merit, 0.03 ml / l of tetra ethyl lead (TEL: tetra ethyl lead) was added to the mixture with a performance index of 130.1 when 0.01 ml / l of tetra ethyl lead (TEL) It can be easily corrected with a high performance index of 131.1. Accordingly, it can be seen that the air gasoline composition according to the embodiment satisfies the specifications according to the experimental items of ASTM D910 (Grade 100 / Grade 100LL / Grade 100VLL) and Def-Stan 91-90, which are the international standards of aviation gasoline.

In particular, it has been confirmed that the air-fuel gasoline composition according to the embodiment maintains the 39.9 kPa Reid Vapor Pressure (RVP) while maintaining the motor octane number of 100.9, thereby improving safety and combustion performance .

It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (11)

Light alkylates;
Mixed C5 oil fractions containing linear C5 paraffins and C5 olefins; And
An aerospace gasoline composition comprising an aromatic compound,
Wherein the content of the aromatic compound is 0.1% by volume to 5% by volume of the air gasoline composition,
The hard aluminate and the mixed C5 oil fraction comprise from 75 vol% to 95 vol% of the hard alcoholate and from 5 vol% to 25 vol% of the mixed C5 oil, based on 100 vol% of the air gasoline composition other than the aromatic compound doing
Air gasoline composition.
delete The method according to claim 1,
Wherein the air gasoline composition further comprises 0.01 ml to 0.53 ml of tetra ethyl lead per liter (TEL: tetra ethyl lead)
Air gasoline composition.
The method according to claim 1,
When the boiling point of the hard-boiled alkylate is 170 占 폚 or lower
Air gasoline composition.
The method according to claim 1,
The mixed C5 oil fraction may be pyrolysed naphtha cracked residual oil, hydrocracked naphtha cracked residual oil or fluidized catalytic cracking (FCC)
Air gasoline composition.
The method according to claim 1,
The linear C5 paraffin and the C5 olefin have a volume ratio of 15:85 to 95: 5
Air gasoline composition.
The method according to claim 1,
The C5 olefin is preferably selected from the group consisting of 1-pentene, 2-pentene, 2-methyl-1-butene, 2-butene, 1,3-pentadiene, 1,4-pentadiene, 2,3-pentadiene, cyclopentene, cyclopentene, cyclopentadiene, and a mixture thereof.
Air gasoline composition.
The method according to claim 1,
The aromatic compound may be selected from the group consisting of benzene, toluene, xylene, ethylbenzene, aniline, toluidine, phenol, cresol, ≪ / RTI >
Air gasoline composition.
The method according to claim 1,
Wherein the motor octane number of the air gasoline composition is 99.6 or more
Air gasoline composition.
The method according to claim 1,
Wherein the air gasoline composition has a Reid Vapor Pressure (RVP) of 38.0 kPa to 49.0 kPa
Air gasoline composition.
The method according to claim 1,
When the performance number of the air gasoline composition is 130.0 or more
Air gasoline composition.

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