JP6403622B2 - Jet fuel composition and method for producing the same - Google Patents

Description

  The present invention relates to a jet fuel composition excellent in thermal stability and a method for producing the same.

  Thermal stability is recognized as one of the important characteristics in jet fuel. It is known that fuels with poor thermal stability produce rubbery or solid hydrocarbons through decomposition and polymerization. These not only adhere to the subsequent parts as dirt, but also cause local high-temperature areas and turbine damage, so various improvement methods have been proposed (see Patent Documents 1 and 2).

Special table 2013-535563 gazette JP-T 2009-511699

  The present invention has been developed in view of the above-described present situation, and an object of the present invention is to provide a jet fuel composition having more excellent thermal stability.

  As a result of intensive studies on the above problems, the present inventors have completed the present invention.

That is, the present invention has an aromatic hydrocarbon content of 11 to 25% by volume, a 50% by volume distillation temperature of 175 to 215 ° C, a 90% by volume distillation temperature of 210 to 300 ° C, and 15 ° C. A jet fuel base material having a density of 0.78 to 0.82 g / cm ³ , a sulfur content of 3000 ppm by mass or less, a Saybolt color of 12 to 30 and satisfying the following formula: To a jet fuel composition.
−0.04 × T50 (° C.) + 0.04 × T90 (° C.) + 0.001 × sulfur content (mass ppm) −0.15 × aromatic content (volume%) − 0.26 × Saebold color + 10 <1
(In the formula, T50 is a 50 volume% distillation temperature measured according to JIS K 2254, T90 is a 90 volume% distillation temperature measured according to JIS K 2254, and a sulfur content is a sulfur content measured according to JIS K 2541-6, aromatic. The minute is an aromatic hydrocarbon content measured according to JIS K 2536-1, and the Saybolt color is the Saybolt color measured according to JIS K 2580.)

  Further, the present invention provides the jet fuel composition as described above, wherein the jet fuel base material is obtained by hydrorefining a raw material oil containing a catalytic cracking kerosene fraction distilled from a catalytic cracking apparatus. About.

  In addition, the present invention provides one or more other kerosene distillates in which the jet fuel base is distilled from a normal pressure distillation apparatus, a direct desulfurization apparatus, or an indirect desulfurization apparatus to a catalytic cracking kerosene fraction distilled from a catalytic cracking apparatus. The above-described jet fuel composition is obtained by hydrorefining a feedstock oil further containing a component.

  The present invention also relates to the jet fuel composition as described above, wherein the catalytic cracking kerosene fraction is contained in an amount of 1 to 16% by volume based on the total amount of the feedstock.

In the present invention, the aromatic hydrocarbon content is 11 to 25% by volume, the 50% by volume distillation temperature is 175 to 215 ° C, the 90% by volume distillation temperature is 210 to 300 ° C, and 15 ° C. A density of 0.78 to 0.82 g / cm 3, a sulfur content of 3000 ppm by mass or less, a Saybolt color of 12 to 30, and a jet fuel base material satisfying the following formula: The present invention relates to a method for producing a jet fuel composition.
−0.04 × T50 (° C.) + 0.04 × T90 (° C.) + 0.001 × sulfur content (mass ppm) −0.15 × aromatic content (volume%) − 0.26 × Saebold color + 10 <1
(In the formula, T50 is a 50 volume% distillation temperature measured according to JIS K 2254, T90 is a 90 volume% distillation temperature measured according to JIS K 2254, and a sulfur content is a sulfur content measured according to JIS K 2541-6, aromatic. The minute is an aromatic hydrocarbon content measured according to JIS K 2536-1, and the Saybolt color is the Saybolt color measured according to JIS K 2580.)

  Further, the present invention provides the jet fuel composition as described above, wherein the jet fuel base material is obtained by hydrorefining a raw material oil containing a catalytic cracking kerosene fraction distilled from a catalytic cracking apparatus. It relates to the manufacturing method.

  In addition, the present invention provides one or more other kerosene distillates in which the jet fuel base is distilled from a normal pressure distillation apparatus, a direct desulfurization apparatus, or an indirect desulfurization apparatus to a catalytic cracking kerosene fraction distilled from a catalytic cracking apparatus. The method for producing a jet fuel composition as described above, which is obtained by hydrorefining a feedstock further containing a component.

  The present invention also relates to the method for producing a jet fuel composition as described above, wherein the catalytic cracking kerosene fraction is contained in an amount of 1 to 16% by volume based on the total amount of the feedstock.

  According to the present invention, it is possible to predict in advance the thermal stability that could not be measured without actually producing a jet fuel composition, and to provide a jet fuel composition having superior thermal stability compared to the prior art. Can do.

  Hereinafter, the present invention will be specifically described.

  The jet fuel composition of the present invention contains a jet fuel base material having the following properties.

The aromatic hydrocarbon content of the jet fuel base material according to the present invention needs to be 11 to 25% by volume, and preferably 19 to 25% by volume. If the aromatic hydrocarbon content is less than 11% by volume, the decomposition / polymerization product cannot be dissolved, which is not preferable, and if it exceeds 25% by volume, the combustion characteristics are deteriorated.
Unless otherwise specified in the present invention, the aromatic hydrocarbon content is determined according to JIS K 2536-1 “Petroleum product-component test method Part 1: Fluorescent indicator adsorption method”.

  The 10% by volume distillation temperature (T10) of the jet fuel substrate according to the present invention is preferably 160 to 200 ° C, more preferably 160 to 180 ° C. If the 10% by volume distillation temperature is less than 160 ° C, the flash point will be too low, which is not preferable, and if it exceeds 200 ° C, the flammability in the engine will be adversely affected.

  The 50% by volume distillation temperature (T50) of the jet fuel substrate according to the present invention needs to be 175 to 215 ° C, and preferably 180 to 210 ° C. If the 50% by volume distillation temperature is less than 175 ° C, it is not preferable because the heavy component is concentrated and the decomposition / polymerization product is concentrated by increasing the volatilization amount of the light component. However, it is not preferable because decomposition and polymerization easily occur.

  The 90 volume% distillation temperature (T90) of the jet fuel substrate according to the present invention needs to be 210 to 300 ° C, and preferably 220 to 275 ° C. If the 90% by volume distillation temperature is less than 210 ° C, it is not preferable because a sufficient calorific value cannot be maintained, and if it exceeds 300 ° C, the heavy component increases and decomposition / polymerization easily occurs.

  Unless otherwise specified in the present invention, these distillation properties (T10, T50, and T90) are determined according to JIS K 2254 “Petroleum products-distillation test method”.

Density at 15 ℃ jet fuel base stock according to the present invention is required to be ^{0.78~0.82g / cm 3, 0.79~0.81g / cm} 3 are preferred. It is not preferable because the density at 15 ℃ calorific value is lowered to volume and less than 0.78 g / cm ^3, undesirably exceeds 0.82 g / cm ³ heavy fraction is likely to occur is increased decomposition and polymerization .
Unless otherwise specified in the present invention, the density at 15 ° C. is determined according to JIS K2249-1 “Crude oil and petroleum products—Determination of density—Part 1: Vibration method”.

The sulfur content of the jet fuel base material according to the present invention needs to be 3000 ppm by mass or less, preferably 700 ppm by mass or less, and more preferably 10 ppm by mass or less. If the sulfur content exceeds 3000 mass ppm, the decomposition / polymerization reaction is promoted, which is not preferable.
Unless otherwise specified in the present invention, the sulfur content is determined according to JIS K 2541-6 “Crude oil and petroleum products—Sulfur content test method Part 6: Ultraviolet fluorescence method”.

The Saybolt color of the jet fuel substrate according to the present invention needs to be 12 to 30, preferably 19 to 30, and more preferably 28 to 30. A Saybolt color of less than 12 is not preferable because polycyclic aromatics increase, causing decomposition / polymerization reaction to deteriorate thermal stability, and a value exceeding 30 is not preferable because it cannot be measured.
In the present invention, unless otherwise specified, the Saybolt color is determined by “JIS K 2580 petroleum product-color test method”.

The jet fuel base material according to the present invention needs to satisfy the following equation in order to improve thermal stability, that is, the “thermal stability parameter” defined on the left side of the following equation must be less than 1.
−0.04 × T50 [° C.] + 0.04 × T90 [° C.] + 0.001 × sulfur content [mass ppm] −0.15 × aromatic content [volume%] − 0.26 × Saebold color + 10 <1
(In the formula, T50 is a 50 volume% distillation temperature measured according to JIS K 2254, T90 is a 90 volume% distillation temperature measured according to JIS K 2254, and a sulfur content is a sulfur content measured according to JIS K 2541-6, aromatic. The minute is an aromatic hydrocarbon content measured according to JIS K 2536-1, and the Saybolt color is the Saybolt color measured according to JIS K 2580.)

A method for deriving the equation will be described below.
It is assumed that the thermal stability of jet fuel is correlated with other properties, but other properties are also correlated with each other, so it is not appropriate to obtain a correlation equation by ordinary multiple regression analysis from the viewpoint of collinearity. Absent. Therefore, in the present invention, GA-PLS (genetic algorithm-partial least square method) which is one of statistical analysis methods is used.

  First, PLS will be described. PLS is also called a least square method, and sets a variable group called a score between an explanatory variable and an objective variable. Since the scores are sequentially calculated so that they are orthogonal to each other, it is possible to perform regression analysis while avoiding collinearity. For example, for details, see Yukihiro Ozaki et al., “Multivariate Analysis for Chemists—Introduction to Chemometrics” p. 42-70 etc.

GA is also called a genetic algorithm. Although PLS can use a larger number of data sets than explanatory variables, even if unnecessary explanatory variables are included, even if R ² indicating the correlation becomes high, it is calculated by the leave-one-out method and predicted. Q ^2, which is an index indicating sex, tends to decrease. By using GA, it is possible to select the explanatory variable group such as to increase the Q ^2. More specifically, the use / non-use of each explanatory variable is assigned as 1 and 0, respectively, and the use / non-use of the entire explanatory variable group is expressed in a form such as 10111010. It performed PLS in each group of variables used to calculate the ^{Q 2.} Two of these combinations of variable groups are selected as parents, and combinations of variables used as children by crossing and mutation are generated by regarding the use / nonuse combinations such as 10111010... As gene sequences. To calculate their Q ² 'again, to generate a re-child as a parent in the next generation those with high Q ^2. By repeating this, GA is a method for outputting variable combination candidates with high predictability. This method is incorporated in ChemInfoNavi's statistical analysis software “Chemish”.

Using GA-PLS installed in ChemInfoNavi's statistical analysis software “Chemish”, the explanatory variables are general properties of jet fuel, 34 types of composition data by gas chromatography, etc., and the target variable is the test temperature 290 Statistical analysis was performed based on 67 data sets, with the JFTOT tube deposition degree at ° C.
JFTOT tube deposition is measured based on JIS K 2276 Petroleum Products-Aviation Fuel Oil Test Method, but it is not the lowest temperature in the test method, 260 ° C. The degree of deposition was measured. In addition, JFTOT tube deposition degree includes integer values such as 0, 1, 2, 3, 4 and numbers such as less than 1, but less than 1 is converted to 0.5, and less than 1 is converted to 1.5. Analysis was performed.

  According to GA, the explanatory variables of the JFTOT tube deposition degree at the test temperature of 290 ° C, which is the objective variable, are 50 vol% distillation temperature, 90 vol% distillation temperature, sulfur content, aromatic hydrocarbon content, and Saybolt color. I was able to squeeze it. Table 1 shows all 67 data on the JFTOT tube deposition degree at 290 ° C., which are these five explanatory variables and objective variables.

As a result of this analysis, an equation indicating the above-mentioned “thermal stability parameter” is obtained, and the square value R ² of the correlation coefficient with the JFTOT tube deposition degree at 290 ° C. is 0.810, calculated by the leave-one-out method. the predictability ^{Q 2} to which was a 0.769 showed good correlation.

The thermal stability is usually judged by the JFTOT tube deposition degree, and the standard specifies that the JFTOT tube deposition degree at 260 ° C. <3, but if the JFTOT tube deposition degree at 290 ° C. <1, the thermal stability is more stable. It can be said that it is an excellent jet fuel. Since the thermal stability parameter has a good correlation with the JFTOT tube deposition degree, it is determined that the thermal stability parameter is less than 1, that is, jet fuel having excellent thermal stability by satisfying the following formula. it can.
−0.04 × T50 (° C.) + 0.04 × T90 (° C.) + 0.001 × sulfur content (mass ppm) −0.15 × aromatic content (volume%) − 0.26 × Saebold color + 10 <1
As a result, conventionally, when jet fuel is produced by blending two or more kinds of base materials, the thermal stability cannot be known unless it is blended. It became possible to estimate the thermal stability.

  Here, the 50 vol.% Distillation temperature is a parameter indicating that if the light component is too much, the heavy component is concentrated by volatilization and the concentration of the decomposition / polymerization product becomes high. It is a parameter indicating that decomposition and polymerization products are likely to be generated when there is too much mass. The sulfur content is a substance that causes decomposition and polymerization reactions. Aromatic hydrocarbons improve thermal stability by dissolving purified decomposition and polymerization products. The Saebold color is correlated with the amount of a small amount of polycyclic aromatics, and is a parameter indicating that the polycyclic aromatics cause degradation / polymerization reaction and deteriorate thermal stability.

  The jet fuel base material according to the present invention can be obtained by hydrorefining raw material oil containing a catalytic cracking kerosene fraction distilled from a catalytic cracking apparatus. The feed oil other than the catalytic cracking kerosene fraction is not particularly limited, and those usually used as feed oil for a jet fuel base material can be used.

  In the present invention, the catalytic cracking device continuously contacts heavy oil as a raw material oil in a fluidized state under specific operating conditions, cracks the heavy oil into light hydrocarbons, It is an apparatus for fractionating the obtained hydrocarbons for each desired fraction.

  The catalytic cracking conditions in the catalytic cracking apparatus are not particularly limited as long as a catalytic cracking kerosene fraction having predetermined properties can be obtained, but the reaction temperature is 450 to 630 ° C. in the presence of the catalytic cracking catalyst, and the catalyst / oil ratio. Is preferably 3 to 20 (mass / mass).

  The catalytic cracking catalyst is not particularly limited, but a catalyst composed of a matrix composed of zeolite as an active ingredient and its supporting matrix is usually used. The matrix is composed of an active matrix, a binder (such as silica), a filler (such as clay mineral), and other components (such as rare earth metal oxides and metal trap components). Here, the active matrix has decomposition activity, and examples thereof include alumina and silica alumina.

  Although the raw material oil of the said catalytic cracking apparatus is not specifically limited, It is mainly heavy oil. Examples of heavy oils include straight-run gas oil, vacuum gas oil, atmospheric residue, vacuum residue, pyrolysis gas oil, and heavy oil obtained by hydrorefining these. These heavy oils may be used alone, or a mixture of these heavy oils or a mixture of these heavy oils with a part of light oil may be used.

In the present invention, the catalytic cracking kerosene fraction is a kerosene fraction distilled from the catalytic cracking device, and the 10% by volume distillation temperature is preferably 130 to 200 ° C, more preferably 140 to 195 ° C. preferable. Further, the lighter the catalytic cracking kerosene fraction is, the more unsaturated aliphatic hydrocarbons are contained. Therefore, the amount of heat generated by hydrogenation is increased during hydrorefining. Therefore, if the 10% by volume distillation temperature of the catalytic cracking kerosene fraction is less than 130 ° C., the risk of runaway in the operation management of the hydrotreating apparatus increases. Further, if the 10% by volume distillation temperature exceeds 200 ° C., it is not preferable because it adversely affects the combustibility of the engine.
Moreover, it is preferable that 90 volume% distillation temperature is 160-300 degreeC, and it is more preferable that it is 170-250 degreeC. If the 90% by volume distillation temperature is less than 160 ° C, the content of unsaturated aliphatic hydrocarbons increases due to lightening, and the amount of heat generated during desulfurization increases, increasing the risk of runaway. This is not preferable because heavy components increase and decomposition and polymerization are likely to occur.

  In the present invention, the kerosene fraction hydrorefined together with the catalytic cracking kerosene fraction is not particularly limited, but is a straight-run kerosene or direct desulfurization obtained by distilling crude oil or the like in an atmospheric distillation unit. Examples include direct de-kerating oil obtained by treating atmospheric residual oil with an apparatus, and intermediate de-kerating oil obtained by treating vacuum gas oil with an indirect desulfurization apparatus.

In the present invention, the hydrorefining conditions in the production of the jet fuel base material are not particularly limited as long as a jet fuel base material having a predetermined property can be obtained. It is preferably 330 ° C., reaction pressure 1.5 to 5.0 MPa, LHSV 0.5 to 5.0 h ⁻¹ , and hydrogen / oil ratio 50 to 300 Nm ³ / KL.

  The hydrorefining catalyst is not particularly limited, but a porous inorganic oxide containing alumina is used as a support, and at least one of cobalt, nickel, molybdenum, and tungsten is used as an active component. preferable.

In the present invention, the ratio of the catalytic cracking kerosene distilled from the catalytic cracking apparatus to the total amount of raw material oil is preferably 1 to 16% by volume, more preferably 3 to 16% by volume.
It is known that the catalytic cracking kerosene fraction has a higher aromatic hydrocarbon content than straight-run kerosene and the like. Therefore, when the mixing amount of the catalytic cracking kerosene fraction is less than 1% by volume, a sufficient aromatic hydrocarbon content cannot be obtained. When the aromatic hydrocarbon content is low, the solubility of the decomposition / polymerization product is inferior, and rubbery or solid hydrocarbons are likely to be produced. Further, since the catalytic cracking kerosene fraction contains a large amount of unsaturated aliphatic hydrocarbons, it causes an increase in the amount of heat generated by hydrogenation during hydrorefining. Therefore, if the mixing amount of the catalytic cracking kerosene fraction exceeds 16% by volume, the risk of runaway increases in the operation management of the hydrotreating apparatus.

The jet fuel composition of the present invention needs to satisfy JIS aviation turbine fuel oil standards. Here, the JIS aviation turbine fuel oil standard is a standard that satisfies the requirements of JIS K 2209. JIS aviation turbine fuel oil standards include a total acid value of 0.1 mgKOH / g or less, a flash point of 38 ° C. or more, a kinematic viscosity at −20 ° C. of 8 mm ² / s or less, a true calorific value of 42.8 MJ / kg or more, and a real gum of 7 mg. / 100 ml or less.

  The jet fuel composition of the present invention may contain various additives in addition to the jet fuel base as necessary. Examples of the additive include an antioxidant, a conductivity adjusting agent, a metal deactivator, and an antifreezing agent. Although the addition amount of these additives is arbitrary, the total addition amount is 0.5 volume% or less with respect to a jet fuel composition, and 0.2 volume% or less is preferable.

  The above description is merely an example of the embodiment of the present invention, and various modifications can be made according to the description of the scope of claims.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.
In addition, each property in an Example was performed based on the above-mentioned test method and a measuring method.

  By treating crude oil with an oil refining process, straight-run kerosene distilled from an atmospheric distillation unit was obtained. The properties are shown in Table 2.

  Moreover, the catalytic cracking kerosene fraction distilled out from the above-mentioned catalytic cracking apparatus was obtained. The cracker was operated at a reaction temperature of 530 ° C. and a catalyst / oil ratio of 5.0 (mass / mass). Table 2 shows the properties of the catalytic cracking kerosene fraction.

(Examples 1-4, Comparative Examples 1-4)
A catalytic cracking kerosene fraction is mixed with the above-mentioned straight-run kerosene at a ratio shown in Table 3, using a hydrorefining apparatus, a reaction temperature of 300 to 320 ° C., a reaction pressure of 3.5 MPa, LHSV 3.0 h ⁻¹ , hydrogen A jet fuel base material was obtained by processing under conditions of an oil ratio of 150 Nm ³ / kL. About the obtained jet fuel base material, a property was measured and the result is shown in Table 3.

  From the results in Table 3, it was found that the jet fuel base material obtained in each example was excellent in the JFTOT tube deposition degree measured at 290 ° C. On the other hand, the jet fuel base materials obtained in Comparative Examples 1 to 4 are not mixed with the catalytic cracking kerosene fraction distilled from the catalytic cracking apparatus, and the JFTOT tube deposition degree measured at 290 ° C. exceeds 1. It was found that the thermal stability was poor.

(Example 5)
A total of 0.1% by volume of an antioxidant, a conductivity modifier and an anti-icing agent was mixed with Example 1 to obtain a jet fuel composition. The obtained composition had a total acid value of 0.01 mg KOH / g, a flash point of 43 ° C., a kinematic viscosity at −20 ° C. of 3.507 mm ² / s, a true calorific value of 43.0 MJ / kg, and a real gum of 2 mg / 100 ml. And met the standards for jet fuel.

According to the present invention, the raw material is a mixture of a catalytic cracking kerosene fraction distilled from a catalytic cracking device with a straight-run kerosene distilled from an atmospheric distillation device, and hydrorefining this to produce a quality It is very useful industrially because a jet fuel composition excellent in the above can be obtained.

Claims (7)

The aromatic hydrocarbon content is 11 to 25 vol%, the 50 vol% distillation temperature is 175 to 215 ° C, the 90 vol% distillation temperature is 210 to 300 ° C, and the density at 15 ° C is 0.78. A jet fuel composition comprising a jet fuel base material having a sulfur content of 3000 ppm by mass or less, a Saybolt color of 12 to 30, and satisfying the following formula: ˜0.82 g / cm ³ .
−0.04 × T50 (° C.) + 0.04 × T90 (° C.) + 0.001 × sulfur content (mass ppm) −0.15 × aromatic content (volume%) − 0.26 × Saebold color + 10 <1
(In the formula, T50 is a 50 volume% distillation temperature measured according to JIS K 2254, T90 is a 90 volume% distillation temperature measured according to JIS K 2254, and a sulfur content is a sulfur content measured according to JIS K 2541-6, aromatic. The minute is an aromatic hydrocarbon content measured according to JIS K 2536-1, and the Saybolt color is the Saybolt color measured according to JIS K 2580.)   2. The jet fuel composition according to claim 1, wherein the jet fuel base material is obtained by hydrorefining a feed oil containing a catalytic cracking kerosene fraction distilled from a catalytic cracking apparatus. 3.   The jet fuel base material further comprises one or more other kerosene fractions distilled from the atmospheric distillation unit, direct desulfurization unit, and indirect desulfurization unit in the catalytic cracking kerosene fraction distilled from the catalytic cracking unit The jet fuel composition according to claim 1, wherein the jet fuel composition is obtained by hydrorefining the fuel.   The jet fuel composition according to claim 2 or 3, wherein the catalytic cracking kerosene fraction is contained in an amount of 1 to 16% by volume based on the total amount of the feedstock. Aromatic hydrocarbon content obtained by hydrorefining feedstock containing the catalytic cracking kerosene fraction distilled from the catalytic cracking unit is 11 to 25% by volume, and 50% by volume distillation temperature is 175 to 215. , 90 vol% distillation temperature is 210 to 300 ° C, density at 15 ° C is 0.78 to 0.82 g / cm3, sulfur content is 3000 mass ppm or less, and Saybolt color is 12 to 12 A method for producing a jet fuel composition, comprising a jet fuel base material satisfying the following formula:
−0.04 × T50 (° C.) + 0.04 × T90 (° C.) + 0.001 × sulfur content (mass ppm) −0.15 × aromatic content (volume%) − 0.26 × Saebold color + 10 <1
(In the formula, T50 is a 50 volume% distillation temperature measured according to JIS K 2254, T90 is a 90 volume% distillation temperature measured according to JIS K 2254, and the sulfur content is a sulfur content measured according to JIS K 2541-6, aromatic. The minute is an aromatic hydrocarbon content measured according to JIS K 2536-1, and the Saybolt color is the Saybolt color measured according to JIS K 2580.) The jet fuel base material further comprises one or more other kerosene fractions distilled from the atmospheric distillation unit, direct desulfurization unit, and indirect desulfurization unit in the catalytic cracking kerosene fraction distilled from the catalytic cracking unit The method for producing a jet fuel composition according to claim 5, wherein the method is obtained by hydrorefining the fuel. The method for producing a jet fuel composition according to claim 5 or 6 , wherein the catalytic cracking kerosene fraction is contained in an amount of 1 to 16% by volume based on the total amount of the feedstock oil.