JP2016124896A - Kerosene base material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a kerosene base material that has improved combustibility and a high calorific value and can be suitably used in heating equipment or the like such as oil stove and oil fan heater.SOLUTION: The kerosene base material is provided that has a distillation characteristics in which a 5% volumetric distillation temperature is 150°C or more in the, 95% volumetric distillation temperature is 250°C or less, and 97% volumetric distillation temperature is 260°C or less, and that has a flash point of 40°C or more, a density at 15°C of 0.790 g/cmmore and 0.845 g/cmor less, a kinematic viscosity at 30°C of 1.0 mm/s or more and 1.7 mm/s or less, a sulfur content of less than 5 mass ppm, a bromine index of 150 mgBr/100 g or less, a gross calorific value of 37000 kJ/L or more, a smoke point of 21 mm or more, a peroxide value of 1 mass ppm or less, a nitrogen content of 1 mass ppm or less, a proportion of cycloparaffins of 42% or more (ionic strength), a proportion of cycloparaffins with 2 or more rings of 10% or more (ionic strength), and a proportion of total aromatics of 1% or more and 20% or less (ionic strength).SELECTED DRAWING: None

Description

  The present invention relates to a kerosene base material, and more particularly to a high calorific value kerosene base material with improved combustibility, which is suitably used in heating equipment such as an oil stove and an oil fan heater.

  Since the fuel for petroleum combustion equipment used for household combustion equipment such as stoves and water heaters is insufficient in the winter season of demand, hydrodesulfurization is expanded by expanding the boiling range of the kerosene fraction of conventional atmospheric distillation equipment. By doing so, kerosene production is being increased. However, this method changes the supply balance from gasoline to light oil, and it becomes difficult to flexibly cope with changes in the demand structure of gasoline and light oil. Further, if the kerosene fraction is largely cut from light oil, there will be a problem with the low temperature fluidity of the light oil, so it is difficult to significantly increase the production of kerosene.

  Also, there is a so-called GTL (Gas to liquid) kerosene, which is prepared with the same distillation characteristics as petroleum-based kerosene and uses natural gas as a raw material and does not contain sulfur or aromatics produced by Fischer-Tropsch synthesis. Has been put on the market. However, in order to produce GTL kerosene, energy investment is large and production equipment cost and operation cost are both large. Therefore, the supply amount is expected to be limited for the time being. Moreover, when GTL kerosene is used for an oil combustion apparatus, there exists a problem that a fuel consumption is large compared with petroleum type kerosene.

  On the other hand, hydrocracking base materials such as cracked diesel oil (LCO) produced from fluid catalytic cracking equipment (FCC equipment) and coker diesel oil produced from coker equipment that become surplus due to sluggish demand for heavy oil, and direct distillation Measures to increase kerosene production, such as mixing with kerosene, are being considered. However, the kerosene fraction obtained by these hydrocracking has a high aromatic content and low smoke point, so there is a problem in combustibility such as soot being easily generated when burned in a stove. There is a problem that the amount is limited (see, for example, Patent Documents 1 and 2).

JP 2003-105349 A JP 2009-292857 A

  The present invention has basic performance suitable as a kerosene base material from petroleum-based hydrocarbons such as LCO and coker diesel oil, and has low sulfur, high calorific value, excellent combustibility, and alone, other kerosene such as straight-run kerosene. An object of the present invention is to provide a high-grade kerosene base material that contributes to increased production of kerosene in winter that can be used even when mixed with the base material. In addition, a method for producing a kerosene composition by mixing the kerosene base material with another kerosene base material as necessary is provided.

  As a result of intensive studies to achieve the above object, the inventors of the present invention are suitable as a kerosene base material because the base material obtained by specific processing of a specific raw material contains many compounds having a specific structure. It has been found that kerosene having basic performance, low sulfur, high calorific value, and excellent combustibility can be produced, and the present invention has been completed.

That is, the present invention has a distillation property of 5% volume distillation temperature of 150 ° C. or higher, 95% volume distillation temperature of 250 ° C. or lower, 97% volume distillation temperature of 260 ° C. or lower, and flash point of 40 ° C. or higher. The density at 15 ° C. is 0.790 g / cm ³ or more and 0.845 g / cm ³ or less, the kinematic viscosity at 30 ° C. is 1.0 mm ² / s or more and 1.7 mm ² / s or less, the sulfur content is less than 5 ppm by mass, bromine index is 150mgBr ₂ / 100g or less, the total calorific value 37000kJ / L or more, the smoke point above 21 mm, peroxide value less than 1 mass ppm, the nitrogen content is less than 1 mass ppm, the ratio of cycloparaffins is more than 42% (Ionic strength) The present invention relates to a kerosene base material in which the proportion of two or more cycloparaffins is 10% or more (ionic strength) and the total aromatics are 1% or more and 20% or less (ionic strength).

  In the present invention, the proportion of alkylbenzenes is 15% or less (ionic strength), the proportion of monocyclic naphthenobenzenes is 5% or less (ionic strength), bicyclic naphthenobenzenes, naphthalenes, acenaphthene and biphenyls. In addition, the present invention relates to the above kerosene base material in which the total proportion of fluorenes and phenanthrenes is 0.4% or less (ionic strength) and the proportion of n-paraffins is 12% or less (ionic strength).

  Furthermore, in the present invention, 95% by volume distillation temperature is 270 ° C. or less and flash point is 40, characterized by mixing 1 to 100% by volume of the kerosene base and 0 to 99% by volume of the other kerosene base. The present invention relates to a method for producing a kerosene composition having a temperature of at least C, a sulfur content of 10 ppm by mass or less, and a smoke point of 21 mm or more.

  According to the present invention, it has basic performance suitable as a kerosene base material, and has low sulfur, high calorific value, and excellent combustibility, and can be used alone or mixed with other kerosene base materials such as straight-run kerosene. It is possible to provide a high-grade kerosene composition that contributes to an increase in kerosene production in winter.

  The present invention will be described below.

  The 5 vol% distillation temperature (T5) in the distillation properties of the kerosene base material of the present invention is 150 ° C. or higher, preferably 155 ° C. or higher, more preferably 160 ° C. or higher. When T5 is less than 150 ° C., there is an influence on safety due to a decrease in flash point, which is not preferable. On the other hand, from the viewpoint of maintaining ignition characteristics at low temperatures, it is preferably 190 ° C. or lower, and more preferably 185 ° C. or lower.

  The 95 vol% distillation temperature (T95) in the distillation properties of the kerosene base material of the present invention is 250 ° C or lower, preferably 245 ° C or lower, and more preferably 240 ° C or lower. When T95 exceeds 250 ° C., the smoke point decreases, and soot tends to be generated when used in a core-type stove.

  The 97 vol% distillation temperature (T97) in the distillation properties of the kerosene base material of the present invention is 260 ° C or lower, preferably 255 ° C or lower, more preferably 250 ° C or lower. When T97 exceeds 260 ° C., the smoke point is lowered and soot tends to be generated when used in a core-type stove.

  The distillation properties of the kerosene base material of the present invention need only satisfy T5, T95, and T97 as described above, but the initial boiling point, T10, T30, T50, T70, T90, and the end point have the following properties. Is preferred.

  The initial boiling point in the distillation properties of the kerosene base material of the present invention is preferably 145 ° C. or higher, and more preferably 150 ° C. or higher, from the viewpoint of safety due to reduction in flash point. On the other hand, from the viewpoint of maintaining ignition characteristics at low temperatures, it is preferably 180 ° C. or lower, and more preferably 175 ° C. or lower.

  The 10 vol% distillation temperature (T10) in the distillation properties of the kerosene base material of the present invention is preferably 160 ° C or higher, more preferably 165 ° C or higher, from the viewpoints of odor and calorific value during refueling. . On the other hand, from the viewpoint of maintaining ignitability at low temperatures, it is preferably 195 ° C. or lower, and more preferably 190 ° C. or lower.

  The 30% by volume distillation temperature (T30) in the distillation properties of the kerosene base material of the present invention is preferably 165 ° C or higher, more preferably 170 ° C or higher, from the viewpoint of odor and calorific value during refueling. . On the other hand, from the viewpoint of maintaining ignitability at low temperatures, it is preferably 200 ° C. or lower, and more preferably 195 ° C. or lower.

  The 50 vol% distillation temperature (T50) in the distillation properties of the kerosene base material of the present invention is preferably 170 ° C or higher, more preferably 175 ° C or higher, from the viewpoint of calorific value. On the other hand, from the viewpoint of combustibility, it is preferably 210 ° C. or lower, and more preferably 205 ° C. or lower.

  The 70 vol% distillation temperature (T70) in the distillation properties of the kerosene substrate of the present invention is preferably 175 ° C or higher, more preferably 180 ° C or higher, from the viewpoint of the amount of heat generated. On the other hand, from the viewpoint of combustibility, it is preferably 220 ° C. or lower, more preferably 215 ° C. or lower.

  The 90 volume% distillation temperature (T90) in the distillation properties of the kerosene base material of the present invention is preferably 240 ° C. or lower, more preferably 235 ° C. or lower, from the viewpoint of combustibility.

  The end point in the distillation properties of the kerosene base material of the present invention is preferably 270 ° C. or less, more preferably 260 ° C. or less, from the viewpoint of combustibility.

  Unless otherwise specified in the present invention, the initial boiling point, T5, T10, T30, T50, T70, T90, T95, T97, and the end point are JIS K2254 “Petroleum products—Distillation test method—Atmospheric pressure method”, respectively. It means a value measured by “distillation test method”.

The flash point of the kerosene base material of the present invention is 40 ° C. or higher, preferably 41 ° C. or higher, and more preferably 42 ° C. or higher. When the flash point is less than 40 ° C., it is not preferable from the viewpoint of handling safety. On the other hand, from the viewpoint of ignitability at low temperatures, it is preferably 60 ° C. or lower.
In the present invention, unless otherwise specified, it means a value measured by a sealed tag type of JIS K2265 “How to find a flash point”.

Density at 15 ℃ kerosene substrate of the present invention, 0.790 g / cm ³ or more 0.845 g / cm ³ or less, is preferably not more than 0.795 g / cm ³ or more 0.840 g / cm ^3, More preferably, it is 0.800 g / cm ³ or more and 0.835 g / cm ³ or less. When the density at 15 ° C. is less than 0.790 g / cm ³ , it is not preferable from the viewpoint of the fuel consumption rate, and when it exceeds 0.845 g / cm ³ , it is not preferable from the viewpoint of combustibility.
Unless otherwise specified in the present invention, the density at 15 ° C. means a value measured according to JIS K2249 “Crude oil and petroleum products—Determination of density”.

Kinematic viscosity at 30 ° C. kerosene substrate of the present invention is less 1.0 mm ² / s or more 1.7 mm ² / s, preferably not more than 1.1 mm ² / s or more 1.65 mm ² / s More preferably, it is 1.2 mm ² / s or more and 1.6 mm ² / s or less. When the kinematic viscosity at 30 ° C. is less than 1.0 mm ² / s, it is not preferable from the viewpoint of penetration into the core in the core type stove, while when it exceeds 1.7 mm ² / s, the core type is used. It is not preferable from the viewpoint of the kerosene sucking speed in the stove.
Unless otherwise specified in the present invention, the kinematic viscosity at 30 ° C. means a value measured by JIS K2283 “Crude oil and petroleum products—Kinematic viscosity test method and viscosity index calculation method”.

The kerosene base material of the present invention has a sulfur content of less than 5 ppm by mass, preferably 3 ppm by mass or less, and more preferably 1 ppm by mass or less. As the sulfur content increases, the odor tends to become relatively strong, and is preferably less than 5 ppm by mass from the viewpoint of suppressing sulfur oxides in the combustion exhaust gas.
Unless otherwise specified in the present invention, the sulfur content means a value measured by JIS K2541 “Crude oil and petroleum products—sulfur content test method”.

Bromine Index of kerosene substrate of the present invention is less 150mgBr ₂ / 100g, preferably not more than 130mgBr ₂ / 100g, and more preferably less 120mgBr ₂ / 100g. Preferably it does not exceed 150mgBr 2 _/ 100g since there is a tendency that tar is easily generated in the nozzle in the core and fan heaters when bromine index is higher in the core stove.
Unless otherwise specified in the present invention, the bromine index means a value measured by the “bromine index test method” in the appendix of JIS K 2605 “bromine number test method”.

The total calorific value of the kerosene base material of the present invention is 37000 kJ / L or more, preferably 37100 kJ / L or more, more preferably 37200 kJ / L or more from the viewpoint of reducing fuel consumption. On the other hand, from the viewpoint of balance with other properties, it is preferably 39000 kJ / L or less.
Unless otherwise specified in the present invention, the total calorific value means a value measured according to JIS K 2279 “Crude oil and petroleum products—a calorific value test method and a calculation estimation method”.

The smoke point of the kerosene base material of the present invention is 21 mm or more, preferably 22 mm or more, and more preferably 23 mm or more. When the smoke point is less than 21 mm, it is not preferable from the viewpoint of preventing soot generation and incomplete combustion in the core type stove. On the other hand, from the viewpoint of balance with other properties, it is preferably 35 mm or less.
Unless otherwise specified in the present invention, the smoke point means a value measured by JIS K2537 “Petroleum products—kerosene and aviation turbine fuel oil—smoke point test method”.

The peroxide value of the kerosene base material of the present invention is preferably 1 mass ppm or less. When the peroxide value exceeds 1 ppm by mass, there is a concern of poor combustion due to the generation of tar.
Unless otherwise specified in the present invention, the peroxide value means a value measured by the Petroleum Institute method JPI-5S-46-96 “Testing method for kerosene peroxide value”.

The nitrogen content of the kerosene base material of the present invention is preferably 1 mass ppm or less. When the nitrogen content exceeds 1 mass ppm, it is not preferable from the viewpoint of increasing harmful substances.
In the present invention, the nitrogen content means a value measured by JIS K2609 “Crude oil and petroleum products—nitrogen content test method” unless otherwise specified.

  The ratio of cycloparaffins in the kerosene base material of the present invention is 42% or more (ionic strength), preferably 50% or more (ionic strength), and more preferably 60% or more (ionic strength). 70% or more (ionic strength) is more preferable. When the ratio of cycloparaffins is less than 42% (ionic strength), the total calorific value decreases.

  The ratio of two or more cycloparaffins in the kerosene base material of the present invention is 10% or more (ionic strength), preferably 15% or more (ionic strength), and 20% or more (ionic strength). It is more preferable. When the ratio of cycloparaffins having two or more rings is less than 10% (ionic strength), the total calorific value is lowered.

The ratio of the total aromatic content in the kerosene base material of the present invention is 1% to 20% (ionic strength), preferably 1.5% to 18% (ionic strength), and preferably 2% or more. It is more preferably 15% or less (ionic strength). When the ratio of the total aromatic content is less than 1% (ionic strength), the total calorific value decreases, which is not preferable. When the ratio exceeds 20% (ionic strength), the smoke point decreases, which is not preferable.
The total aromatic content here means the total content of aromatic hydrocarbon types such as alkylbenzenes, naphthenobenzenes, naphthalenes, acenaphthene / biphenyls, fluorenes, and phenanthrenes described later. .

  The proportion of alkylbenzenes in the kerosene base material of the present invention is 15.0% or less (ionic strength), preferably 12.5% or less (ionic strength), and 10.0% or less (ionic strength). It is more preferable that When the proportion of alkylbenzenes exceeds 15.0% (ionic strength), the smoke point decreases, and soot tends to be generated when used in a core-type stove.

  The ratio of monocyclic naphthenobenzenes in the kerosene base material of the present invention is 5% or less (ionic strength), preferably 4% or less (ionic strength), and 3% or less (ionic strength). It is more preferable. When the proportion of naphthenobenzenes exceeds 5% (ionic strength), the smoke point is lowered, and soot tends to be generated when used in a core-type stove.

  The total proportion of naphthenobenzenes (bicyclic naphthenobenzenes), naphthalenes, acenaphthene / biphenyls, fluorenes, and phenanthrenes having one benzene ring and two naphthene rings in the kerosene base material of the present invention. Is 0.4% or less (ionic strength), preferably 0.3% or less (ionic strength), and more preferably 0.2% or less (ionic strength). When the total ratio exceeds 0.4% (ionic strength), the smoke point is lowered, and soot tends to be easily generated when used in a core-type stove.

  The ratio of n-paraffins in the kerosene base material of the present invention is 12% or less (ionic strength), preferably 10% or less (ionic strength), and more preferably 5% or less (ionic strength). It is preferably 2% or less (ionic strength). When the ratio of n-paraffins exceeds 12% (ionic strength), the total calorific value decreases.

  Unless otherwise specified in the present invention, hydrocarbon types such as cycloparaffins, alkylbenzenes, naphthenobenzenes, naphthalenes, acenaphthene / biphenyls, fluorenes, and phenanthrenes are as follows: This is obtained as a result of GC / TOFMS analysis and hydrocarbon type analysis on the saturated and aromatic components obtained by silica gel chromatography fractionation.

[GC / TOFMS analysis]
(Separation conditions)
Silica gel: Wakosil C200 36g
Sample amount: 1.6 g
Saturated solvent: n-pentane 100mL
Aromatic content elution solvent: diethyl ether 80mL
Solvent removal: Rotary evaporator (30 ° C water bath)
(GC condition)
Column: ZB-1MS (30m × φ0.25mm, 0.25μm-film) manufactured by phenomenonex
Oven temperature: 50 ° C (5 min hold)-(5 ° C / min) → 230 ° C-(20 ° C / min) → 340 ° C
Injection method: Split Injection temperature: 340 ° C
GC interface temperature: 350 ° C
Carrier gas: He
Carrier gas flow rate: 1.4 mL / min (constant)
(TOFMS conditions)
Apparatus: JMS-T100GC manufactured by JEOL Ltd.
Counter electrode voltage: -10 kV
Ionization method: FI (field ionization)
Ion source temperature: Room temperature
Mass number measurement range: m / z 35-500

The kerosene sample was subjected to mass spectrometry under the above conditions, and each peak was classified from the obtained mass spectrum by the type of C _n H _{2n + z} , and each ratio (% (ionic strength)) was obtained as a percentage of molecular ionic strength.
Here, in formula C _n H _{2n + z} , z = + 2 is paraffins, z = 0 is monocyclic cycloparaffins, z = -2 is bicyclic cycloparaffins, z = -4 is tricyclic cycloparaffins, z = -6 is defined as alkylbenzenes, z = -8 is defined as monocyclic naphthenobenzenes such as tetrahydronaphthalene, and z = -10 is defined as bicyclic naphthenobenzenes such as octahydrophenanthrene.
In addition, n-paraffins in paraffins belong to each other by the GC measurement time, and the ratio is obtained.

  The kerosene base material of the present invention is obtained by hydrodesulfurizing petroleum hydrocarbons having an aromatic content of 50% by volume or more, a 10% distillation temperature of 140 ° C. or more, and a 95% distillation temperature of 380 ° C. or less. Hydrogenation obtained by contacting a hydrocracking catalyst carrying one or more active metals selected from Group 6, Group 9 and Group 10 metals under a hydrogen partial pressure of 10 to 14 MPa It is preferably produced by fractionating cracked oil.

  Examples of petroleum hydrocarbons include cracked light oil (LCO) produced from a fluid catalytic cracking device (FCC device) and coker light oil produced from a coker device.

The aromatic content of the petroleum hydrocarbon is 50% by volume or more, 60% by volume or more, or 80% by volume or more. In the production method according to the present embodiment, a petroleum-based hydrocarbon having a higher aromatic content can more easily obtain a high-quality kerosene base material. The aromatic hydrocarbon content of the petroleum hydrocarbon may be 100% by volume, 95% by volume or less, or 90% by volume or less.
Unless otherwise specified in the present invention, the aromatic content is the total aromatics measured by the Petroleum Institute method JPI-5S-49-97 “Petroleum products—hydrocarbon type test method—high performance liquid chromatograph”. Mean content of minutes.

  The 10% volume distillation temperature of petroleum hydrocarbons is 140 ° C or higher, preferably 160 ° C or higher. Those having a 10% distillation temperature of less than 140 ° C. are not preferable because they become lighter than the kerosene fraction due to hydrocracking. Moreover, the 10% volume distillation temperature of petroleum-based hydrocarbons may be 250 ° C. or lower, or 230 ° C. or lower.

  The 95% volume distillation temperature of petroleum hydrocarbons is 380 ° C. or lower, preferably 360 ° C. or lower. In addition, the 95% capacity distillation temperature of petroleum hydrocarbons may be 300 ° C. or higher, or 330 ° C. or higher.

  The petroleum-based hydrocarbon may contain a sulfur content. The sulfur content of the petroleum hydrocarbon may be, for example, 0.2% by mass or more, and may be 0.4% by mass or more, but the hydrocracking catalyst in the latter stage in the hydrodesulfurization process in the former stage. It is necessary to perform desulfurization to sufficiently suppress poisoning due to sulfur content.

  Petroleum hydrocarbons may also contain nitrogen. The nitrogen content of the petroleum hydrocarbon may be, for example, 200 mass ppm or more, or 500 mass ppm or more. In the production method according to the present embodiment, even if nitrogen content is included in such a content, since the nitrogen content can be sufficiently removed in the hydrodesulfurization step, the hydrocracking catalyst is sufficiently poisoned by the nitrogen content. Can be suppressed. Further, the nitrogen content of the petroleum hydrocarbon is preferably 1500 ppm by mass or less, more preferably 1000 ppm by mass or less from the viewpoint of economy.

  Petroleum hydrocarbons may each contain, as an aromatic component, a one-ring aromatic component, a two-ring aromatic component, and three or more aromatic components. In the petroleum hydrocarbon, the content ratio of each aromatic component is not particularly limited. For example, the petroleum hydrocarbon is 10 to 50% by volume (preferably 10 to 40% by volume) of monocyclic aromatics and 20 to 60% by volume of bicyclic aromatics (preferably 10 to 40% by volume) based on the total amount of petroleum hydrocarbons. (Preferably 20 to 50% by volume) may contain 0 to 20% by volume (preferably 5 to 15% by volume) of an aromatic component of 3 or more rings.

Petroleum hydrocarbons may further contain components other than those described above, such as olefins. The olefin content of the petroleum hydrocarbon may be, for example, 0 to 10% by volume or 1 to 5% by volume.
In the present invention, unless otherwise specified, the 1-ring aromatic content, 2-ring aromatic content, 3-ring or more aromatic content, and olefin content are determined by the Japan Petroleum Institute Law JPI-5S-49-97 “Petroleum Products”. It means the content of monocyclic aromatics, bicyclic aromatics, tricyclic or higher aromatics and olefinic hydrocarbons as measured by “Hydrocarbon type test method—high performance liquid chromatograph”.

The density of the petroleum hydrocarbon is not particularly limited, and for example, the density at 15 ° C. may be 0.88 to 0.96 g / cm ³ .

  Hydrodesulfurization of petroleum hydrocarbons can be performed, for example, by bringing petroleum hydrocarbons into contact with a hydrorefining catalyst in the presence of hydrogen. The hydrorefining catalyst is used, for example, in a fixed bed reactor.

  The hydrodesulfurization conditions can be appropriately changed according to the sulfur content of the petroleum-based hydrocarbon, and a known hydrorefining catalyst can be appropriately selected and used as the hydrorefining catalyst.

  The hydrotreating catalyst may be, for example, a carrier containing at least one selected from metals of Group 13, Group 14, and Group 15 (Aluminum, Silicon, Phosphorus, and Boron) of the Periodic Table, Group 6 of the Periodic Table, The catalyst may support at least one active metal selected from Group 9 and Group 10 metals (molybdenum, cobalt, nickel).

The hydrogen partial pressure in hydrodesulfurization can be set to 3 to 15 MPa, for example, and may be set to 10 to 14 MPa. Moreover, the reaction temperature in hydrodesulfurization can be 250-450 degreeC, for example, and it is preferable to set it as 270-410 degreeC. Moreover, the liquid space velocity (LHSV; Liquid Hourly Space Velocity) in hydrodesulfurization can be 0.2-4.0h < ^-1 >, for example, and can also be 0.2-3.0h < ^-1 >. Furthermore, the hydrogen / oil ratio in the hydrodesulfurization may be a 160~1280Nm ³ / kL, can be a 240~800Nm ³ / kL. By performing hydrodesulfurization under such conditions, a higher quality kerosene fraction tends to be easily obtained.
When petroleum-based hydrocarbons are circulated through a reaction apparatus in which a hydrorefining catalyst and a hydrocracking catalyst are laminated, it is preferable that the hydrogen partial pressure is 10 to 14 MPa and the reaction temperature is 250 to 355 ° C. .

  Hydrodesulfurized oil is applied to a hydrocracking catalyst in which one or more active metals selected from metals of Group 6, Group 8, Group 9 and Group 10 of the periodic table are supported on a support containing USY-type zeolite. The hydrocracked oil can be obtained by contacting under a hydrogen partial pressure of 10 to 14 MPa.

  The carrier of the hydrocracking catalyst is a carrier containing USY-type zeolite. USY-type zeolite is obtained by ultra-stabilizing Y-type zeolite by hydrothermal treatment and / or acid treatment. USY-type zeolite has a fine pore structure inherent to Y-type zeolite. This fine pore structure is a structure composed of micropores having a pore diameter of 2 nm or less. Further, in addition to the fine pore structure described above, new pores having a pore diameter of 2 to 10 nm are formed in the USY-type zeolite.

  The average particle size of the USY zeolite is not particularly limited, but is preferably 1.0 μm or less, more preferably 0.5 μm or less. Further, the silica / alumina molar ratio (molar ratio of silica to alumina) in the USY-type zeolite is preferably 10 to 200, more preferably 15 to 100, and further preferably 20 to 60.

  The support of the hydrocracking catalyst may further contain an amorphous composite metal oxide such as silica alumina, silica zirconia and alumina boria. The carrier is preferably a carrier comprising USY zeolite and one or more amorphous composite metal oxides selected from the group consisting of silica alumina, silica zirconia, and alumina boria. And one or more amorphous composite metal oxides selected from the group consisting of silica alumina and alumina boria are more preferable.

  The hydrocracking catalyst has at least one selected from metals of Group 6, Group 8, Group 9 and Group 10 of the periodic table as the active metal supported on the carrier. Here, the periodic table refers to a periodic table of long-period elements based on the provisions of IUPAC (International Pure Applied Chemistry Association). Specific examples of these metals include noble metals such as platinum, palladium, rhodium, ruthenium, iridium and osmium, cobalt, nickel, molybdenum, tungsten and iron.

  The hydrocracking catalyst preferably has at least one selected from the group consisting of platinum, palladium, nickel, cobalt, molybdenum and tungsten as the active metal, and is selected from the group consisting of cobalt, nickel, molybdenum and tungsten. It is more preferable to have one or more. Further, the active metal may have platinum and / or palladium. Furthermore, it is also preferable to use a combination of a plurality of these metals. In this case, preferred combinations include platinum-palladium, cobalt-molybdenum, nickel-molybdenum, nickel-cobalt-molybdenum, nickel-tungsten, and the like.

  In hydrocracking, hydrodesulfurization oil is brought into contact with the above hydrocracking catalyst under a hydrogen partial pressure of 10 to 14 MPa to perform hydrocracking. The method of bringing the desulfurized oil into contact with the hydrocracking catalyst can be performed by various methods such as a fixed bed flow type, a fluidized bed type, and a moving bed type. It is preferable to carry out by a flow type.

When carrying out the hydrogenolysis in the flow reactor, hydrogen / oil ratio may be, for example 120~800Nm ³ / KL, it is preferable that the ^{160~720Nm 3 / KL, 200~640Nm 3 /} KL More preferably. The liquid hourly space velocity this time is, for example 0.1~5.0h be a ^-1 is preferably 0.2～3.0H ^-1, in 0.3～1.0H ^-1 More preferably. Moreover, the temperature of hydrocracking can be 250-355 degreeC, for example, It is preferable to set it as 270-355 degreeC, It is more preferable to set it as 280-350 degreeC, It is further preferable to set it as 300-350 degreeC. preferable. By performing hydrocracking under such conditions, a kerosene base material with a large amount of cycloparaffin and a high calorific value can be obtained.

The hydrodesulfurization reaction apparatus and hydrocracking reaction apparatus according to the present invention may be arranged in series so as to allow continuous oil passage. In this case, LHSV of the sum of these reactors (total LHSV) may be a 0.1～5.0H ^-1, it is preferably 0.2~3.0h ^-1, 0.3 more preferably ~1.0h ^-1, further preferably 0.3~0.6h ^-1. By performing hydrodesulfurization and hydrocracking under such conditions, a kerosene base material with a further reduced sulfur content can be obtained.

  The kerosene substrate of the present invention can be used as kerosene as it is, but if necessary, it may be mixed with one or more other kerosene substrates to produce a kerosene composition. Other kerosene base materials include petroleum kerosene base materials such as straight-run kerosene and hydrogen, which are produced by distilling crude oil at atmospheric pressure to obtain a kerosene fraction and then removing sulfur by hydrodesulfurization. Examples include kerosene base materials such as GTL kerosene synthesized from carbon oxide. When the kerosene base material of the present invention is mixed with other kerosene base materials, the mixing ratio is arbitrary, but the ratio of the kerosene base material of the present invention is preferably 1% by volume or more, and a higher calorific value is obtained. From the viewpoint of obtaining, it is more preferably 10% by volume or more, and further preferably 15% by volume or more. Although there is no restriction | limiting in particular about an upper limit, For example, it can be 99 volume% or less, and it is good also as 95 volume% or less, and good also as 90 volume% or less.

  The kerosene composition according to the present invention preferably has the following properties.

  The 95 vol% distillation temperature (T95) in the distillation properties of the kerosene composition according to the present invention is preferably 270 ° C or lower, and more preferably 268 ° C or lower. When T95 exceeds 270 ° C., the smoke point decreases and soot tends to be generated when used in a core-type stove.

  The flash point of the kerosene composition according to the present invention is 40 ° C. or higher, preferably 41 ° C. or higher, and more preferably 42 ° C. or higher. When the flash point is less than 40 ° C., it is not preferable from the viewpoint of handling safety.

  The kerosene composition according to the present invention has a sulfur content of 10 ppm by mass or less, preferably 5 ppm by mass or less, and more preferably 1 ppm by mass or less. As the sulfur content increases, the odor tends to become relatively strong, and it is preferable not to exceed 10 mass ppm from the viewpoint of suppressing sulfur oxides in the combustion exhaust gas.

  The smoke point of the kerosene composition according to the present invention is 21 mm or more, preferably 22 mm or more, and more preferably 23 mm or more. When the smoke point is less than 21 mm, it is not preferable from the viewpoint of preventing soot generation and incomplete combustion in the core type stove.

The kerosene composition according to the present invention may contain various additives in addition to the kerosene base as necessary. Additives include antioxidants such as phenolic and amine compounds, metal deactivators such as Schiff and thioamide compounds, surface ignition agents such as organophosphorus compounds, alkenyl succinimides, polyalkylamines, poly Detergents such as ether amines, anti-freezing agents such as polyhydric alcohols and their ethers, alkali metal salts or alkaline earth metal salts of organic acids, sulfates of higher alcohols, 1-methoxy-2-acetoxypropane, etc. Examples thereof include an antistatic agent such as a flame retardant, an anionic surfactant, a cationic surfactant and an amphoteric surfactant, a colorant such as an azo dye, and a discriminating agent such as coumarin. These additives can be used alone or in combination of two or more. Although the addition amount of these additives is arbitrary, the total addition amount is preferably 0.5% by mass or less, more preferably 0.05% by mass or less, with respect to the total amount of the kerosene composition.
As said additive, what was synthesize | combined according to the conventional method may be used, and a commercially available additive may be used. In addition, the additive currently marketed may have diluted the active ingredient which contributes to the effect which the additive aimed at with the appropriate solvent. When using a commercially available additive in which the active ingredient is diluted, it is preferable to add the commercially available additive so that the content of the active ingredient in the kerosene composition falls within the above range.

  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.

(Hydrotreating catalyst)
A commercially available catalyst (support: alumina and silica, active metal: nickel and molybdenum) was used as the hydrorefining catalyst.

(Hydrocracking catalyst)
<Preparation of carrier>
Water was added to a mixture of 50% by mass of USY-type zeolite and 40% by mass of alumina binder and kneaded into a clay, and 10% by mass of boric acid was added and further kneaded to prepare a kneaded product. This kneaded product was molded into a cylindrical shape having a diameter of about 1.5 mm and a length of about 3 mm by extrusion molding. The obtained molded body was dried at 120 ° C. for 3 hours and further calcined in air at 500 ° C. for 3 hours to obtain a carrier.

<Preparation of catalyst>
Nickel nitrate and ammonium tungstate were dissolved in ion-exchanged water corresponding to the pre-measured water absorption of the carrier to obtain an impregnation solution. The impregnating solution is impregnated into the support by an initial wetting method so that the Ni content in terms of oxide is 8% by mass and the W content in terms of oxide is 20% by mass based on the mass of the support. Went. Next, the obtained impregnated product (catalyst precursor) was dried at 120 ° C. for 3 hours and then calcined at 500 ° C. for 1 hour under an air stream to obtain a hydrocracking catalyst.

Example 1
The cracked light oil 1 having the composition shown in Table 1 was passed through a reaction apparatus in which a hydrorefining catalyst and a hydrocracking catalyst were stacked, and hydrodesulfurization and hydrocracking were performed to obtain a hydrocracked oil. In the reactor, the reaction pressure for hydrodesulfurization and hydrocracking was 13.5 MPa, the reaction temperature was 345 ° C., and the total LHSV was 0.42 h ⁻¹ .
Next, a kerosene base material A was obtained by fractionating a kerosene fraction from the obtained hydrocracked oil, and its properties were determined.

(Example 2)
A kerosene base material B was obtained in the same manner as in Example 1 except that the cracked light oil 1 was changed to the cracked light oil 2 shown in Table 1, and the properties thereof were determined.

Example 3
The conditions of the reactor in which cracked light oil 1 was changed to cracked light oil 2 listed in Table 1 and hydrodesulfurization and hydrocracking were carried out were as follows: reaction pressure 10.5 MPa, reaction temperature 330 ° C., total LHSV = 0.55 h ^{− A} kerosene base material C was obtained in the same manner as in Example 1 except that it was changed to 1, and the properties thereof were obtained.

(Comparative Example 1)
A kerosene base material D was obtained in the same manner as in Example 3 except that the reaction pressure in the reactor in which hydrodesulfurization and hydrocracking were performed was changed to 8.0 Mpa, and the properties thereof were obtained.

(Comparative Example 2)
A kerosene base material E was obtained in the same manner as in Example 1 except that the reaction temperature in the reactor subjected to hydrodesulfurization and hydrocracking was changed to 362 ° C. and total LHSV = 0.72 h ^−1. Asked.

(Comparative Example 3)
A kerosene base material F was obtained in the same manner as in Example 3 except that the reaction temperature in the reactor subjected to hydrodesulfurization and hydrocracking was changed to 358 ° C. and total LHSV = 0.63 h ⁻¹ , and its properties Asked.

(Reference example)
Commercial kerosene (reference kerosene G) was purchased and its properties were determined.

  Table 2 shows properties of kerosene (kerosene base materials A to C, kerosene base materials D to F, and reference kerosene G) obtained in Examples and Comparative Examples.

Example 4
A kerosene composition was prepared by mixing 50% by volume of kerosene base A obtained in Example 1 and 50% by volume of a straight-run kerosene base having a boiling range of 150 to 264 ° C. obtained by atmospheric distillation of Middle Eastern crude oil. . The obtained kerosene composition had a 95% by volume distillation temperature of 231 ° C., a flash point of 44 ° C., a sulfur content of 1 mass ppm, a smoke point of 25 mm, and a total calorific value of 37014 kJ / L.

  The kerosene bases A to C of Examples 1 to 3, which are kerosene bases of the present invention, all had a very low sulfur content, a high smoke point, and a high total calorific value.

The present invention has basic performance suitable as kerosene, has a very low sulfur content, has good flammability, and therefore has excellent environmental performance, high calorific value, and alone, other kerosene such as straight-run kerosene. Since it provides a kerosene base material that can be used even when mixed with a base material, it can be suitably used as a kerosene composition that contributes to increased production of kerosene in winter.

Claims (3)

In the distillation properties, the 5% volume distillation temperature is 150 ° C. or more, the 95% volume distillation temperature is 250 ° C. or less, the 97% volume distillation temperature is 260 ° C. or less, the flash point is 40 ° C. or more, and the density at 15 ° C. 0.790 g / cm ³ or more and 0.845 g / cm ³ or less, kinematic viscosity at 30 ° C. of 1.0 mm ² / s or more and 1.7 mm ² / s or less, sulfur content of less than 5 mass ppm, bromine index of 150 mgBr ₂ / 100 g or less, total calorific value is 37000 kJ / L or more, smoke point is 21 mm or more, peroxide value is 1 mass ppm or less, nitrogen content is 1 mass ppm or less, and the ratio of cycloparaffins is 42% or more (ionic strength), 2 A kerosene base material in which the ratio of cycloparaffins having a ring or higher is 10% or more (ionic strength) and the total aromatics is 1% to 20% (ionic strength).   The proportion of alkylbenzenes is 15% or less (ionic strength), the proportion of monocyclic naphthenobenzenes is 5% or less (ionic strength), bicyclic naphthenobenzenes, naphthalenes, acenaphthene / biphenyls, fluorenes, phenanthrenes 2. The kerosene base material according to claim 1, wherein the total proportion of saponification is 0.4% or less (ionic strength) and the proportion of n-paraffins is 12% or less (ionic strength). A 95 vol% distillation temperature characterized by mixing 1 to 100 vol% of kerosene base material according to claim 1 or 2 and 0 to 99 vol% of another kerosene substrate, and having a flash point of 40 or less. A method for producing a kerosene composition having a sulfur content of 10 ppm by mass or less and a smoke point of 21 mm or more.