JP2015193770A - Kerosene composition, and preparation method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a kerosene composition capable of allowing a heating instrument to be operated stably over a long period of time, and to provide a preparation method of the kerosene composition.SOLUTION: The kerosene composition of the present invention is characterized in that a ratio of naphthenic hydrocarbons to the total of the saturated hydrocarbon content, which consists of paraffinic hydrocarbons and naphthenic hydrocarbons, and the aromatic hydrocarbon content is equal to or higher than 10 mass% and lower than 34 mass% and the ratio of the aromatic hydrocarbon content thereto is equal to or higher than 10 mass% and lower than 29 mass%. The preparation method of the kerosene composition comprises a step of bringing a starting oil, which is obtained by mixing a catalytically-cracked light gas oil (HVN) or an oil sand-derived kerosene fraction in straight-run kerosene (KERO), into contact with a catalyst bed formed by using a hydrorefining catalyst to hydrorefine the starting oil and further comprises another step of bringing another starting oil, which is obtained by mixing a catalytically-cracked gas oil (LCO) in heavy gas oil (HGO), vacuum heavy gas oil (VGO) or a mixed product of the heavy gas oil and the vacuum heavy gas oil, into contact with the catalyst bed formed by using the hydrorefining catalyst to hydrorefine the starting oil.

Description

  TECHNICAL FIELD The present invention relates to a kerosene composition and a method for producing the kerosene composition, and more particularly to a kerosene composition suitably used for heating equipment such as a petroleum stove and a petroleum fan heater, and a method for producing the same.

  Various improvements have been made to the kerosene composition in order to obtain a kerosene composition suitable for use in heating equipment such as an oil stove and an oil fan heater. As such a refined kerosene composition, for example, a fuel composition for oil-burning equipment that has good ignitability and combustibility and low fuel consumption (see, for example, Patent Document 1), improved oxidation stability Kerosene composition (see, for example, Patent Document 2), kerosene composition with excellent storage stability (see, for example, Patent Document 3), low-sulfur kerosene that can stably operate heating equipment over a long period of time (for example, Patent Document 4) is known as the prior art.

JP 2011-84675 A JP 2007-77355 A JP-A-2005-290186 JP 2006-348186 A

  Since the kerosene compositions described in Patent Documents 1 to 4 are not evaluated for long-term use (for example, 1000 hours of use), the improved kerosene composition is used for long-term heating equipment. In fact, it is not always possible to operate stably. Then, an object of this invention is to provide the manufacturing method of the kerosene composition which can operate | move a heating apparatus stably over a long period of time, and the kerosene composition.

The present inventors have found that a kerosene composition capable of stably operating a heating device over a long period of time can be obtained by setting the proportion of naphthene and the proportion of aromatics in the kerosene composition within predetermined ranges. Was completed. That is, the present invention is as follows.
In the kerosene composition of the present invention, the proportion of naphthene is 10% by mass or more and less than 34% by mass, and the proportion of aromatic content is 10% by mass with respect to the total of saturated components and aromatic components composed of paraffin and naphthene. More than 29% by mass.
In the present invention, a feed oil obtained by mixing a kerosene fraction obtained by mixing catalytic cracked light diesel oil (HVN) or oil sand-derived kerosene fraction with a straight-run kerosene (KERO) is contacted with a catalyst bed formed using a hydrorefining catalyst. A kerosene composition comprising a step of hydrotreating, wherein straight-run kerosene has the following properties (a) to (c), and catalytically cracked light gas oil has the following (d) to (f) satisfies the properties, respectively, in the inlet of the feedstock in the hydrorefining process, the hydrogen pressure 2MPa least 10MPa or less, the 2h ^-1 or 15h ^-1 or less LHSV, reaction temperature, 200 ° C. or higher 360 ° C. or less, the hydrogen / feedstock The oil ratio was set to 50 nL / L or more and 500 nL / L or less.
(A) The 95% distillation temperature distilled from the atmospheric distillation apparatus in straight-run kerosene is 200 ° C. or higher and 280 ° C. or lower,
(B) the density of the straight run kerosene is at 0.750 g / cm ³ or more 0.850 g / cm ³ or less,
(C) The sulfur content of straight-run kerosene is 0.001% by mass or more and 0.8% by mass or less,
(D) 95% distillation temperature distilled from the catalytic cracking device in the catalytic cracking light diesel oil is 180 ° C. or higher and 270 ° C. or lower,
(E) contacting the density of the cracked light gas oil is at 0.750 g / cm ³ or more 0.900 g / cm ³ or less,
(F) The sulfur content of the catalytically cracked light gas oil is 0.001% by mass or more and 0.08% by mass or less.
Furthermore, the present invention is formed by using a hydrocracking catalyst, a raw oil obtained by mixing a heavy gas oil (HGO), a vacuum heavy gas oil (VGO) or a mixture thereof with a catalytic cracking gas oil (LCO). A method for producing a kerosene composition comprising a step of hydrocracking by contacting a catalyst bed, wherein the heavy gas oil and the vacuum heavy gas oil have the following properties (a) to (c): There satisfy each property below (d) ~ (f), the inlet of the feedstock in the hydrocracking process, higher 3MPa hydrogen pressure 20MPa or less, the LHSV 0.1 h ^-1 or 10h ^-1 or less, the reaction temperature The hydrogen / feed oil ratio was set to 300 nL / L to 2000 nL / L.
(A) The end point of distillation from the atmospheric distillation apparatus or the vacuum distillation apparatus for heavy gas oil and vacuum heavy gas oil is 400 ° C. or more and 600 ° C. or less,
(B) The density of the heavy gas oil and the vacuum heavy gas oil is 0.800 g / cm ³ or more and 1.000 g / cm ³ or less,
(C) The sulfur content of heavy gas oil and reduced-pressure heavy gas oil is 1.0 mass% or more and 3.0 mass% or less,
(D) 90% distillation temperature distilling from the catalytic cracking device in the catalytic cracking light diesel oil is 280 ° C or higher and 390 ° C or lower,
(E) the density of the catalytically cracked light gas oil is 0.800 g / cm ³ or more and 1.000 g / cm ³ or less,
(F) The sulfur content of the catalytically cracked light gas oil is 0.1% by mass or more and 0.8% by mass or less.
Moreover, the kerosene composition of the present invention is produced by the method for producing a kerosene composition of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the kerosene composition which can drive | operate a heating apparatus stably over a long period of time, and the manufacturing method of the kerosene composition can be provided.

FIG. 1 is a graph showing evaluation results of stove combustion tests of kerosene compositions of Examples and Comparative Examples.

  In the kerosene composition of the present invention, the ratio of naphthene is 10% by mass or more and less than 34% by mass, and the ratio of aromatic content is 10% by mass or more with respect to the total of saturated components and aromatic components composed of paraffin and naphthene. It is less than 29% by mass. Hereinafter, the kerosene composition of the present invention will be described in detail.

(Saturated and aromatic content)
Saturates consist of paraffin and naphthene. Paraffin is a saturated chain compound, and paraffin is linear or branched. Naphthene is a compound having a naphthene ring (saturated ring). On the other hand, the aromatic component is a compound having an aromatic ring.

  In the kerosene composition of the present invention, the proportion of naphthene is 10% by mass or more and less than 34% by mass and the proportion of aromatic content is 10% by mass or more with respect to the sum of the saturated and aromatic components consisting of paraffin and naphthene. The proportion of naphthene is 10% by mass or more and 29% by mass or less, and the aromatic content is 10% by mass or more and 28% by mass or less. When the ratio of naphthene is 10% by mass or more and less than 34% by mass and the ratio of aromatic content is 10% by mass or more and 29% by mass or less with respect to the total amount of saturated and aromatic components composed of paraffin and naphthene The kerosene composition can stably operate the heating device over a long period of time. In addition, the ratio of naphthene and the ratio of aromatic content are values measured by two-dimensional gas chromatography.

  The above-mentioned heating equipment is stably operated over a long period of time, for example, after burning a kerosene composition in a heating equipment for 1000 hours, an exhaust gas test, a fuel consumption test, an odor test, an ignition time and a fire extinguishing time test, and a core type It is a success in observing the deterioration of the core of the stove and the nozzle of the fan heater. Each test and deterioration state observation will be described in detail in Examples described later.

  More preferably, when the ratio of naphthene is a mass% and the ratio of aromatic content is b mass% with respect to the total of saturated and aromatic components consisting of paraffin and naphthene, a <−2.525 × The relationship of b + 93.167 is satisfied, and more preferably, the relationship of a ≦ −1.77 × b + 70.07 is satisfied. When the ratio of naphthene and the ratio of aromatic content in the kerosene composition are within the above ranges, the kerosene composition can operate the heating equipment more stably over a long period of time.

  Naphthenes include one-ring naphthenes and two-ring naphthenes. The present inventors have found that, among naphthenes, especially two-ring naphthenes affect the long-term operation of heating equipment. The proportion of the bicyclic naphthene in the saturated component is preferably 1% by mass or more and less than 11% by mass with respect to the total of the saturated component and the aromatic component composed of paraffin and naphthene. When the proportion of the bicyclic naphthene is 1% by mass or more and less than 11% by mass, the kerosene composition can operate the heating device more stably over a long period of time. In addition, the ratio of 1-ring naphthene and 2-ring naphthene is the value measured by two-dimensional gas chromatography.

  The aromatic component includes a monocyclic aromatic component and a bicyclic aromatic component. The present inventors have found that, among aromatic components, the monocyclic aromatic component affects the long-term operation of the heating equipment. The ratio of monocyclic aromatics in the aromatic component is preferably 23% by mass or more and 26% by mass or less with respect to the sum of the saturated component and the aromatic component composed of paraffin and naphthene. When the ratio of the monocyclic aromatic in the aromatic component is 23% by mass or more and 26% by mass or less, the kerosene composition can operate the heating device more stably over a long period of time. In addition, the ratio of the monocyclic aromatic component and the bicyclic aromatic component is a value measured by two-dimensional gas chromatography.

  The aromatic component of one ring includes alkylbenzenes, indanes and tetralins. The present inventors have found that, among monocyclic aromatic components, indans and tetralins in particular affect the long-term operation of heating equipment. The ratio of indans and tetralins in the aromatic component is preferably 1% by mass or more and less than 9% by mass with respect to the total of the saturated component and the aromatic component composed of paraffin and naphthene. When the ratio of indanes and tetralins is 1% by mass or more and less than 9% by mass, the kerosene composition can operate the heating equipment more stably over a long period of time. In addition, the ratio of alkylbenzenes, indanes, and tetralins is a value measured by two-dimensional gas chromatography.

  The smoke point of the kerosene composition of the present invention is preferably 21 mm or more and less than 50 mm, more preferably 23 mm or more and less than 50 mm. In addition, the smoke point of a kerosene composition is the value measured based on JISK2537. When the smoke point is 21 mm or more and less than 50 mm, it is possible to suppress the generation of smoke during the operation of the heating device over a long period of time.

(Properties of kerosene composition)
The kerosene composition of the present invention preferably further has the following properties.
Density: 0.75 g / cm ^{3 to} 0.85 g / cm ³ Boiling range: 140 ° C. to 300 ° C. 95% Distillation temperature: 220 ° C. to 270 ° C. Sulfur content: 80 mass ppm or less Peroxide value: 1 ppm or less Nitrogen content: 1 mass ppm or less Kinematic viscosity at 30 ° C .: 0.9 mm ² / s to 1.7 mm ² / s or less Saybolt color: +25 or more Copper plate corrosion: 1 or less Flash point: 40 ° C. or more

The density is a value measured according to JIS K 2249. When the density is 0.75 g / cm ³ or more and 0.85 g / cm ³ or less, the calorific value of the kerosene composition is increased and the fuel consumption rate is improved. The density is more preferably 0.77 g / cm ³ or more and 0.82 g / cm ³ or less.

  The boiling range is the boiling range of a fraction obtained by distilling crude oil. When the boiling range is 140 ° C. or more and 300 ° C. or less, the combustibility of the kerosene composition is improved. The boiling range is more preferably 145 ° C. or higher and 285 ° C. or lower.

  The 95% distillation temperature is a value measured according to JIS K 2254. When the 95% distillation temperature is 220 ° C. or more and 270 ° C. or less, it is possible to suppress the occurrence of defects due to unburned residue remaining in the core when used in the core type stove. The 95% distillation temperature is more preferably 225 ° C. or higher and 268 ° C. or lower.

  The sulfur content is a value measured according to JIS K2541. Generation | occurrence | production of SOx during combustion can be suppressed as a sulfur content is 80 mass ppm or less. The sulfur content is more preferably 50 ppm by mass or less.

  The peroxide value is a value measured according to JIS K 2276. When the peroxide value is 1 ppm or less, the storage stability of the kerosene composition is improved. The peroxide value is more preferably 0.5 ppm or less.

  The nitrogen content is a value measured by a chemiluminescence method, and is a value measured by a gas chromatography-atomic emission method or a gas chromatography-chemiluminescence method. Generation | occurrence | production of NOx during combustion can be suppressed as nitrogen content is 1 mass ppm or less. The nitrogen content is more preferably 0.5 ppm by mass or less.

The kinematic viscosity at 30 ° C. is a value measured according to JIS K 2283. When the kinematic viscosity at 30 ° C. is 0.9 mm ² / s or more and 1.7 mm ² / s or less, combustible vapor is generated at room temperature, and it is possible to suppress ignition by static electricity and the like, and fuel is generated by capillary action. Even when used as a fuel for a core type stove to be supplied, the fuel can be supplied stably. The kinematic viscosity at 30 ° C. is more preferably 1.0 mm ² / s to 1.6 mm ² / s.

  The Saebold color is a value measured in accordance with JIS K 2580. When the Saybolt color is +25 or more, the kerosene composition can be prevented from being colored and regarded as deteriorated kerosene. The Saybolt color is more preferably +30 or more.

  Copper plate corrosion is a value measured according to JIS K2513. When the copper plate corrosion is 1 or less, the heating equipment can be prevented from being corroded by the kerosene composition.

  The flash point is a value measured in accordance with JIS K 2265 (tag sealed flash point test method). When the flash point is 40 ° C. or higher, combustible vapor is generated at room temperature, and ignition of the kerosene composition due to static electricity or the like can be suppressed. The flash point is more preferably 41 ° C. or higher.

  The smoke point is a value measured according to JIS K 2537. When the smoke point is 21 mm or more, good combustibility can be maintained. The smoke point is more preferably 23 mm or more.

  The volume ratio of aromatic content, 1-ring aromatic content, 2-ring aromatic content, 3-ring aromatic content and unsaturated content in Table 3 is the Petroleum Institute Standard JPI-5S-49-2007 (Petroleum Products-Hydrocarbon Type) (Analysis method—high performance liquid chromatograph (HPLC) method). Good combustibility can be maintained when the aromatic content and the aromatic content of two or more rings are 5% by volume or more and 30% by volume or less and 1% by volume or less, respectively. The aromatic content and the aromatic content of two or more rings are preferably 10% by volume or more and 28% by volume or less and 0.8% by volume or less, respectively.

(Raw material of kerosene composition)
The kerosene composition of the present invention is preferably a kerosene base prepared by hydrocracking heavy gas oil mixed with catalytic cracking gas oil using a hydrocracking apparatus, a kerosene fraction obtained by fractionating and desulfurizing catalytic cracking gas oil, and 1 vol% or more of at least one selected from the group consisting of desulfurized kerosene fraction derived from oil sand is included. More preferably, in the kerosene composition of the present invention, the ratio of kerosene base material prepared by hydrocracking heavy gas oil mixed with catalytic cracking gas oil with a hydrocracking apparatus is 1% by volume or more and less than 40% by volume. More preferably, it is 1% by volume or more and 20% by volume or less, and the ratio of kerosene fraction obtained by fractionating and desulfurizing catalytically cracked diesel oil is 1% by volume or more and less than 15% by volume, more preferably 1% by volume or more and 11% by volume. %, And the proportion of the desulfurized kerosene fraction derived from the oil sand is 1% by volume or more and 15% by volume or less, more preferably 1% by volume or more and 10% by volume or less. By using such a kerosene base or kerosene fraction, a kerosene composition having the above-mentioned naphthene ratio and aromatic content ratio can be obtained.

(Method for producing kerosene composition)
The kerosene composition of the present invention is formed, for example, by using a hydrorefining catalyst, a raw material oil obtained by mixing a kerosene fraction obtained from catalytic cracking light diesel oil (HVN) or oil sand with straight-run kerosene (KERO). It is obtained by a method for producing a kerosene composition comprising a step of hydrotreating by contacting with a catalyst bed (manufacturing method 1 of a kerosene composition). In particular, the hydrorefining treatment can reduce mercaptans that cause odors in the feedstock and aromatics that cause smoke, and improve the corrosivity and color of the feedstock. In this case, preferably, the 95% distillation temperature of distillation from the atmospheric distillation apparatus in straight-run kerosene is 200 ° C. or higher and 280 ° C. or lower, more preferably 220 ° C. or higher and 270 ° C. or lower. is a 0.750 g / cm ³ or more 0.850 g / cm ³ or less, more preferably 0.770 g / cm ³ or more 0.820 g / cm ³ or less, sulfur content of straight run kerosene 0.001% The content is 0.8% by mass or less, and more preferably 0.005% by mass or more and 0.7% by mass or less. In addition, the 95% distillation temperature of distillation from the catalytic cracking device in the catalytic cracking light diesel oil is 180 ° C. or higher and 270 ° C. or lower, more preferably 180 ° C. or higher and 250 ° C. or lower. 750 g / cm ³ or more 0.900 g / cm ³ or less, and more preferably not more than 0.770 g / cm ³ or more 0.880 g / cm ^3, the sulfur content of the catalytically cracked light gas oil than 0.001 wt% 0 0.08% by mass or less, and more preferably 0.001% by mass or more and 0.07% by mass or less. Furthermore, the inlet of the feedstock in the hydrotreating process, hydrogen pressure is less 10MPa or more 2 MPa, more preferably not more than 8MPa than 2.5 MPa, LHSV is at 2h ^-1 or 15h ^-1 or less, more preferably not more than 3h ^-1 or 12h ^-1, reaction temperature is 200 ° C. or higher 360 ° C. or less, and more preferably not more than 340 ° C. 250 ° C. or higher, a hydrogen / feed oil ratio, 50 nL / L or more 500nL / L or less, more preferably 70 nL / L or more and 300 nL / L or less.

  As the hydrorefining catalyst, for example, an alumina catalyst in which molybdenum is supported on an alumina carrier can be used. Further, cobalt, nickel, molybdenum and the like may be used as a promoter metal. The oil sand-derived kerosene fraction is an oil sand synthetic crude oil containing one or more selected from the group consisting of premium Arabian synthetics, sangkor oil sand blend A and cinque sweet blend. It is preferable that it is a kerosene fraction obtained by passing through the oil.

In addition, a raw oil obtained by mixing the kerosene composition of the present invention with heavy light oil (HGO), reduced pressure heavy light oil (VGO) or a mixture thereof with catalytic cracking light oil (LCO) is used with a hydrocracking catalyst. It can also be obtained by a method for producing a kerosene composition comprising a hydrocracking treatment by contacting with a catalyst bed formed in this manner (kerosene composition production method 2). In this case, preferably, the end point of distillation from the atmospheric distillation apparatus or the vacuum distillation apparatus in heavy gas oil and vacuum heavy gas oil is 400 ° C. or more and 600 ° C. or less, more preferably 420 ° C. or more and 580 ° C. or less, the density of the heavy gas oil and vacuum heavy gas oil is at 0.800 g / cm ³ or more 1.000 g / cm ³ or less, more preferably 0.820 g / cm ³ or more 0.950 g / cm ³ or less, heavy The sulfur content of light oil and heavy vacuum oil is 1.0% by mass or more and 3.0% by mass or less, and more preferably 1.5% by mass or more and 2.8% by mass or less. The 90% distillation temperature of the catalytic cracking light gas oil distilled from the catalytic cracking apparatus is 280 ° C. or higher and 390 ° C. or lower, more preferably 300 ° C. or higher and 370 ° C. or lower. 800 g / cm ³ or more 1.000 g / cm ³ or less, and more preferably not more than 0.820 g / cm ³ or more 0.980 g / cm ^3, the sulfur content of the catalytically cracked light gas oil 0.1 wt% 0 0.8 mass% or less, more preferably 0.2 mass% or more and 0.7 mass% or less. Furthermore, the inlet of the feedstock in the hydrocracking process, the hydrogen pressure is less than 20MPa over 3 MPa, more preferably not more than 18MPa over 10 MPa, LHSV is at 0.1 h ^-1 or more 10h ^-1 or less, more preferably not more than 0.3h ^-1 or 5h ^-1, reaction temperature must 300 ° C. or higher 450 ° C. or less, more preferably 360 ° C. or higher 420 ° C. or less, the hydrogen / feedstock ratio of 300 nL / L or more 2000nL / L or less, more preferably 500 nL / L or more and 1000 nL / L or less. In the production of catalytic cracking light oil, the reaction tower outlet temperature of the fluid catalytic cracking apparatus is, for example, 500 ° C. or more and 540 ° C. or less, and the reaction tower pressure is, for example, 0.07 MPaG or more and 0.30 MPaG or less, The ratio is, for example, 4 or more and 30 or less.

  The kerosene composition of the present invention can also be produced by mixing the kerosene composition produced by the above-described kerosene composition production method 1 and the kerosene composition produced by the above-described kerosene composition production method 2. it can.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

[Composition analysis and evaluation method of kerosene composition]
Composition analysis and evaluation in each example and comparative example were performed as follows.
(Composition analysis by two-dimensional gas chromatography)
Using two-dimensional gas chromatography (manufactured by ZOEX, model number: ZOEX KT2006), paraffin, monocyclic naphthene, bicyclic ring with respect to the sum of saturated and aromatic components in the kerosene compositions of Examples and Comparative Examples The proportions of naphthene, tricyclic naphthene, alkylbenzenes, indanes and tetralins, indenes, naphthalenes and biphenyls were measured. In addition, the sum total of the ratio of 1-ring naphthene, 2-ring naphthene, and 3-ring naphthene becomes the ratio of naphthene. In addition, the sum of the ratios of paraffin and naphthene is the ratio of saturation. Furthermore, the sum of the proportions of alkylbenzenes, indanes and tetralins is the proportion of monocyclic aromatics. Further, the sum of the proportions of indenes, naphthalenes and biphenyls is the proportion of the bicyclic aromatic component. Furthermore, the sum of the proportions of the monocyclic aromatic component and the bicyclic aromatic component becomes the aromatic component.

(Composition analysis by high performance liquid chromatography (HPLC))
Using high-performance liquid chromatography (manufactured by Agilent, model number: Agilent 1260), the monocyclic aromatic component and the bicyclic ring with respect to the total of unsaturated components and aromatic components in the kerosene compositions of Examples and Comparative Examples The volume ratio of aromatic content and tricyclic aromatic content was measured. The sum of the proportions of the monocyclic aromatic component, the bicyclic aromatic component, and the tricyclic aromatic component is the aromatic component. Although high-performance liquid chromatography cannot measure naphthene, it has been established as a test method (Petroleum societies standard JPI-5S-49-2007 (petroleum products-hydrocarbon type analysis method-high performance liquid chromatograph method)) and is widely used. It is easy to measure.

(Stove burning test)
Core type stove burned with kerosene composition for a total of 1000 hours (Corona Co., Ltd., model number: SX-246, type: core type, radiation type, ignition method: battery ignition, heating output: 2.42 kW, fuel consumption Quantity: 0.235 L / h, type of core: normal cylindrical core (R-28), nominal size of core: φ65 × 2.8 mm) and fan heater (manufactured by Dainichi Kogyo Co., Ltd., model number: FW-253NES, type : Vaporization type, forced ventilation type, forced convection type, ignition system: continuous discharge ignition, heating output: 2.50 kW, fuel consumption: maximum 0.243 L / h, minimum 0.066 L / h) (hereinafter these are summarized) In some cases, the following items were tested. The heating device was operated for 10 hours a day.

(1) Exhaust gas test Using an exhaust gas analyzer (manufactured by HORIBA, Ltd., model number: NEXA-7000DEGR), exhaust gas generated from the heating device 5 minutes after ignition, 30 minutes after steady combustion The concentrations of CO, CO ₂ , NOx and THC (total hydrocarbons) in the exhaust gas generated from the heating device and in the exhaust gas generated from the heating device were measured for 5 minutes after extinguishing the fire. The average concentration of the measured concentrations was taken as the concentration during ignition of each gas, the concentration during steady combustion, and the concentration during fire extinguishing. When the CO / CO ₂ and NOx of the exhaust gas during steady combustion were 0.002 or less and 90 ppm or less, respectively, and the concentration of THC during ignition was 100 ppm or less, the exhaust gas test was passed. Note that NOx was converted to the minimum combustion time (CO ₂ concentration 15.2%) in accordance with JIS S 3032.

(2) Fuel consumption test The amount of fuel used for one hour in the steady combustion of the heating device was examined. The heating device was set to maximum combustion. When the difference between the fuel consumption for one hour and the rated fuel consumption in the steady combustion of the heating device is within 10% of the rated fuel consumption, the fuel consumption test was passed.

(3) Exhaust gas odor test The exhaust gas odor at the time of ignition, combustion and extinguishing of the heating device was evaluated in five levels by a sensory test with five monitors.
Evaluation stage 1: No feeling Evaluation stage 2: Feeling slightly Evaluation stage 3: Feeling Evaluation stage 4: Feeling slightly strong Evaluation stage 5: Feeling strongly If there are two or more monitors evaluated in evaluation stage 5, the smell of exhaust gas The test passed.

(4) Ignition time, fire extinguishing time In the case of a core-type stove, measure the time from when the type of fire in the heating wire contacts the core until the fire turns around the core, and in the case of a fan heater, the ignition switch The time from when was pressed to when the fire started was measured, and the measured time was taken as the ignition time. In the case of a core-type stove, measure the time until the flame on the core completely disappears after the stove core is set to the normal fire extinguishing position, and in the case of a fan heater, until the fire goes out after the fire switch is pressed Was measured, and the measured time was taken as the fire extinguishing time. In the case of a core-type stove, when the ignition time and the fire extinguishing time are within 10 seconds and within 300 seconds, respectively, in the case of a fan heater, when the ignition time and the fire extinguishing time are within 40 seconds and within 20 seconds, respectively, Time and fire extinguishing time passed.

(5) Observation of deterioration of the core heater and the nozzle of the fan heater The deterioration of the core heater and the nozzle of the fan heater was observed using a magnifying glass. Then, the degree of adhesion of the corktal was examined. If remarkably many coctals were not attached to the core of the core-type stove and the nozzle of the fan heater, the deterioration condition of the core of the core-type stove and the nozzle of the fan heater was passed.

  In addition, when all the above evaluations are passed, it is assumed that the stove combustion test is passed.

[Properties of the used oil]
Table 1 summarizes the properties of the feedstock oil used in each Example and Comparative Example.

Examples 1 and 2 and Comparative Example 1
A light oil base material prepared by hydrocracking a raw oil obtained by mixing 20% by volume of catalytic cracking light oil (LCO) with heavy gas oil (HGO) was added to commercial kerosene at 0% by volume, 20% by volume and 40% by volume. The kerosene compositions of Examples 1 and 2 and Comparative Example 1 were prepared by adding% by volume.

The conditions for hydrocracking treatment are as follows: the end point of distillation from the atmospheric distillation apparatus or the vacuum distillation apparatus for heavy light oil is 540 ° C., the density of heavy light oil is 0.910 g / cm ³ , The sulfur content was 2.20% by mass. Moreover, the 90% distillation temperature distilled from the catalytic cracking device in catalytic cracking light gas oil is 352 ° C., the density of the catalytic cracking light gas oil is 0.940 g / cm ³ , and the sulfur content of the catalytic cracking light gas oil is 0. It was 50 mass%. Furthermore, the hydrogen pressure was 15 MPa, the LHSV was 3 h ⁻¹ , the reaction temperature was 380 ° C., and the hydrogen / feed oil ratio was 700 nL / L at the feedstock inlet in the hydrocracking treatment.

(Example 3 and Comparative Example 2)
The kerosene compositions of Example 3 and Comparative Example 2 were prepared by hydrotreating a raw oil obtained by mixing 11 vol% and 15 vol% catalytic cracked light diesel oil (HVN) with straight-run kerosene (KERO). did.

The conditions of hydrorefining treatment were as follows: 95% distillation temperature from the atmospheric distillation apparatus in straight-run kerosene was 263 ° C., and the density of straight-run kerosene was 0.796 g / cm ³ . The sulfur content was 0.4% by mass. Moreover, the 95% distillation temperature distilled from the catalytic cracking device in the catalytic cracking light gas oil is 223 ° C., the density of the catalytic cracking light gas oil is 0.861 g / cm ³ , and the sulfur content of the catalytic cracking light gas oil is 0. 0.05% by mass. Furthermore, at the inlet of the raw material oil in the hydrorefining treatment, the hydrogen pressure is 5 MPa, the LHSV is 7 h ⁻¹ , the reaction temperature is 290 ° C., and the hydrogen / raw oil ratio is 70 nL / L or more and 80 nL / L. It was the following.

Example 4
A kerosene composition of Example 4 was produced by hydrotreating a raw oil in which a kerosene fraction derived from 10 vol% oil sand was mixed with straight kerosene (KERO).

The conditions of hydrorefining treatment were as follows: 95% distillation temperature from the atmospheric distillation apparatus in straight-run kerosene was 263 ° C., and the density of straight-run kerosene was 0.796 g / cm ³ . The sulfur content was 0.4% by mass. In addition, the 95% distillation temperature of the kerosene fraction derived from the oil sand distilled from the catalytic cracking unit is 263 ° C., and the density of the kerosene fraction derived from the oil sand is 0.840 g / cm ^3. The sulfur content of the kerosene fraction was 0.006% by mass. Furthermore, at the inlet of the feedstock oil in the hydrorefining treatment, the hydrogen pressure is 6 MPa, the LHSV is 7 h ⁻¹ , the reaction temperature is 300 ° C., and the hydrogen / feedstock ratio is 70 nL / L or more and 80 nL / L. It was the following.

  Table 2 shows the results of two-dimensional gas chromatography analysis of the kerosene compositions obtained in each Example and Comparative Example, and Table 3 shows the properties of the kerosene compositions.

  Table 4 and FIG. 1 show the evaluation results of the kerosene compositions obtained in each Example and Comparative Example by the stove combustion test. In Table 4, “core” indicates a core-type stove, and “fan” indicates a fan heater. “OK” indicates that the stove combustion test was passed, and “NG” indicates that the stove combustion test was not passed. Furthermore, in FIG. 1, “◯” indicates that the stove combustion test was passed, and “x” indicates that the stove combustion test was not passed.

  The results shown in Table 4 are summarized in the graph of FIG. From this, it can be seen that all kerosene compositions having a naphthene ratio of less than 34 mass% and an aromatic content ratio of less than 29 mass% have passed the stove combustion test. Moreover, when the ratio of naphthene is a mass% and the ratio of aromatic content is b mass%, all kerosene compositions satisfying the relationship of a <−2.525 × b + 93.167 also pass the stove combustion test. You can see that Furthermore, it can be seen that all kerosene compositions having a naphthene ratio of 29% by mass or less and an aromatic content of 28% by mass or less have also passed the stove combustion test. Moreover, when the ratio of naphthene is a mass% and the ratio of aromatic content is b mass%, all kerosene compositions satisfying the relationship of a ≦ −1.77 × b + 70.07 pass the stove combustion test. You can see that

Claims (15)

  Kerosene having a naphthene ratio of 10% by mass to less than 34% by mass and an aromatic content ratio of 10% by mass to less than 29% by mass with respect to the sum of saturated and aromatic components composed of paraffin and naphthene. Composition.   When the ratio of naphthene is a mass% and the ratio of aromatic content is b mass% with respect to the total of saturated and aromatic components consisting of paraffin and naphthene, a <−2.525 × b + 93.167 The kerosene composition of Claim 1 which satisfy | fills a relationship.   The proportion of naphthene is 10% by mass or more and 29% by mass or less, and the proportion of aromatics is 10% by mass or more and 28% by mass or less, based on the total of saturated and aromatic components composed of paraffin and naphthene. Item 2. A kerosene composition according to Item 1.   When the ratio of naphthene is a mass% and the ratio of aromatic content is b mass% with respect to the total of saturated and aromatic components consisting of paraffin and naphthene, a ≦ −1.77 × b + 70.07 The kerosene composition according to claim 3, which satisfies the relationship.   The ratio of monocyclic aromatics in the aromatic component is 23% by mass or more and 26% by mass or less, based on the total of saturated components and aromatic components composed of paraffin and naphthene. The kerosene composition according to item.   The ratio of the bicyclic naphthene in the saturated component is 1% by mass or more and less than 11% by mass with respect to the total of the saturated component and the aromatic component composed of paraffin and naphthene. The kerosene composition as described in 2.   The ratio of indans and tetralins in the aromatic component is 1% by mass or more and less than 9% by mass with respect to the saturated component and the aromatic component composed of paraffin and naphthene. The kerosene composition according to item 1.   The kerosene composition according to any one of claims 1 to 7, wherein the smoke point is 21 mm or more and less than 50 mm. The density is 0.75 g / cm ³ or more and 0.85 g / cm ³ or less,
The boiling range is 140 ° C. or more and 300 ° C. or less,
95% distillation temperature is 220 ° C. or higher and 270 ° C. or lower,
Sulfur content is 80 mass ppm or less,
The peroxide value is 1 ppm or less,
The nitrogen content is 1 mass ppm or less,
The kinematic viscosity at 30 ° C. is 0.9 mm ² / s to 1.7 mm ² / s,
Saybolt color is +25 or more,
Copper plate corrosion is 1 or less,
The kerosene composition according to any one of claims 1 to 8, having a flash point of 40 ° C or higher.   It consists of a kerosene base made by hydrocracking heavy gas oil mixed with catalytic cracking gas oil using a hydrocracking unit, a kerosene fraction obtained by fractionating and desulfurizing catalytic cracked gas oil, and a desulfurized kerosene fraction derived from oil sands. The kerosene composition according to any one of claims 1 to 9, comprising 1% by volume or more of at least one selected from the group. The ratio of kerosene base material prepared by hydrocracking heavy gas oil mixed with the catalytic cracking gas oil with a hydrocracking apparatus is 1% by volume or more and less than 40% by volume,
The ratio of kerosene fraction obtained by fractionating and desulfurizing the catalytic cracking gas oil is 1% by volume or more and less than 15% by volume,
The kerosene composition according to claim 10, wherein a ratio of the desulfurized kerosene fraction derived from the oil sand is 1 vol% or more and 10 vol% or less. Hydrorefining treatment by bringing raw oil, which is a mixture of straight-run kerosene (KERO) and catalytically cracked light diesel oil (HVN) or kerosene fraction derived from oil sand, into a catalyst bed formed using a hydrorefining catalyst A method for producing a kerosene composition comprising the steps of: wherein the straight-run kerosene satisfies the following properties (a) to (c), and the catalytically decomposed light diesel oil satisfies the properties (d) to (f) below: ,
In the feedstock inlet for the hydrorefining process,
The hydrogen pressure is 2 MPa or more and 10 MPa or less,
LHSV is 2h ^-1 or more and 15h ^-1 or less,
The reaction temperature is 200 ° C. or higher and 360 ° C. or lower,
The hydrogen / raw oil ratio was set to 50 nL / L or more and 500 nL / L or less.
A method for producing a kerosene composition.
(A) The 95% distillation temperature distilled from the atmospheric distillation apparatus in the straight-run kerosene is 200 ° C. or higher and 280 ° C. or lower,
(B) the density of the straight run kerosene is at 0.750 g / cm ³ or more 0.850 g / cm ³ or less,
(C) The straight kerosene has a sulfur content of 0.001% by mass or more and 0.8% by mass or less,
(D) 95% distillation temperature distilled from the catalytic cracking device in the catalytic cracking light gas oil is 180 ° C. or higher and 270 ° C. or lower,
(E) a density of said catalytic cracking light gas oil is not more than 0.750 g / cm ³ or more 0.900 g / cm ^3,
(F) The sulfur content of the catalytically cracked light gas oil is 0.001% by mass or more and 0.08% by mass or less.   Oil sand synthetic crude oil containing one or more selected from the group consisting of premium Arabian synthetic, Sancor oil sand blend A, and cinque sweet blend is passed through an atmospheric distillation apparatus. The method for producing a kerosene composition according to claim 12, which is a kerosene fraction obtained as described above. A raw oil obtained by mixing catalytic cracking gas oil (LCO) with heavy gas oil (HGO), vacuum heavy gas oil (VGO) or a mixture thereof is brought into contact with a catalyst bed formed using a hydrocracking catalyst. A method for producing a kerosene composition comprising a step of hydrocracking,
The heavy gas oil and the vacuum heavy gas oil satisfy the properties (a) to (c) below, and the catalytic cracked light gas oil satisfies the properties (d) to (f) below,
In the feedstock inlet for the hydrocracking treatment,
A hydrogen pressure of 3 MPa to 20 MPa,
A LHSV 0.1h ^-1 more than 10h ^-1 or less,
The reaction temperature is 300 ° C. or more and 450 ° C. or less,
The hydrogen / raw oil ratio was set to 300 nL / L or more and 2000 nL / L or less,
A method for producing a kerosene composition.
(A) The end point of distillation from the atmospheric distillation apparatus or the vacuum distillation apparatus in the heavy gas oil and the vacuum heavy gas oil is 400 ° C. or more and 600 ° C. or less,
(B) The density of the heavy gas oil and the vacuum heavy gas oil is 0.800 g / cm ³ or more and 1.000 g / cm ³ or less,
(C) The sulfur content of the heavy gas oil and the vacuum heavy gas oil is 1.0 mass% or more and 3.0 mass% or less,
(D) 90% distillation temperature distilled from the catalytic cracking device in the catalytic cracking light diesel oil is 280 ° C or higher and 390 ° C or lower,
(E) The density of the catalytically cracked light gas oil is 0.800 g / cm ³ or more and 1.000 g / cm ³ or less,
(F) The catalytically cracked light gas oil has a sulfur content of 0.1% by mass or more and 0.8% by mass or less.   The kerosene composition manufactured by the manufacturing method of the kerosene composition of any one of Claims 12-14.

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