JP4847115B2 - kerosene - Google Patents

Description

  The present invention relates to kerosene, and more particularly to kerosene that is suitably used for heating equipment such as an oil stove and an oil fan heater.

In recent years, as interest in environmental issues has increased socially, in the field of indoor heating equipment, techniques for reducing odorous substances (hydrocarbons, etc.) discharged from the heating equipment are being studied. As a method for reducing odorous substances, improvement of a combustion part of a heating device, installation of an exhaust gas purification device, and the like have been proposed (for example, see Patent Document 1).
On the other hand, it has been reported that if kerosene with poor stability is used over a long period of time, normal combustion is less likely to occur, which may cause a reduction in fuel consumption rate and further cause a malfunction of the apparatus (for example, see Non-Patent Document 1). .) Therefore, it is desirable to use stable kerosene from the viewpoint of reducing odorous substances.
Japanese Patent Publication No.59-16814 Shinichiro Uchida, “PETROTECH”, Petroleum Institute, 1994, Vol. 17, No. 11, p. 37-42

General methods for evaluating the stability of kerosene include methods based on indices such as hue, olefin content, peroxide value, and the like. However, such an evaluation method is not always sufficient in terms of accuracy. Moreover, even if it is kerosene evaluated as having favorable stability based on the said parameter | index, the driving | operation of heating equipment may become unstable.
This invention is made | formed in view of such a situation, and it aims at providing the kerosene which can drive | operate a heating apparatus stably over a long period of time.

  As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that a specific cyclic compound in kerosene has decreased stability, and the above-mentioned compound is suppressed to a specific concentration or less by suppressing this compound. The inventors have found that the problems can be solved and have completed the present invention.

That, kerosene present invention, the proportion of 10% Na Futenobenzen acids or less, 95 vol% distillation temperature in the distillation characteristic is 239.5 to 261.5 ° C., the total number of rings 3 or more naphthenobenzenes the total percentage of the total number of classes and ring 3 or more cycloparaffins 0.6% or less, sulfur content of 10 ppm by mass or less, and the density of 770 kg / ^{m 3} or more 810kg / ^{m 3} or less at 15 ℃ Features.
In addition, the kerosene of the present invention, it is preferable that the ratio of the total number of rings 3 or more naphthenobenzenes compound is below 0.5% or less.

  As described above, the kerosene of the present invention has a ratio of naphthenobenzenes, a ratio of naphthenobenzenes having a total number of rings of 3 or more, and a total ratio of naphthenobenzenes and cycloparaffins having a total number of rings of 3 or more. By satisfying each of the above specific conditions, it was possible to suppress oxidative degradation of kerosene, and further, it was possible to suppress tar generation at relatively high temperatures such as nozzles, resulting in oxidative degradation products. Therefore, the heating device can be stably operated over a long period of time.

In the kerosene of the invention, an initial boiling point of 140 ° C. or higher in distillation characteristics, end point 300 ° C. or less, is 50 vol% distillation temperature of 180 ° C. or higher 230 ° C. or less, a flash point of 40 ° C. or more on, It is preferable that the kinematic viscosity at 30 ° C. is 1.0 to 1.7 mm ² / s, the smoke point is 21 mm or more, and the peroxide value is 1 mass ppm or less.

  Thus, the initial boiling point, end point and 50% by volume distillation temperature, flash point, sulfur content, density at 15 ° C., kinematic viscosity at 30 ° C., smoke point and peroxide value in the distillation properties satisfy the above specific conditions. As a result, the fuel consumption rate of kerosene can be improved, and stability, flammability, safety, and suitability for heating equipment can be improved. Therefore, by using such kerosene for heating equipment, it is possible to improve combustibility, reduce odorous substance emissions, reduce the load on the heating equipment, etc., and as a result, operate the heating equipment more stably. It becomes possible.

  Since the kerosene of the present invention has sufficiently high stability, it becomes possible to perform a stable heating operation over a long period of time by using the kerosene for heating equipment.

Hereinafter, preferred embodiments of the present invention will be described in detail.
The kerosene of the present invention requires that the proportion of naphthenobenzenes be 10% or less, preferably 8% or less, in the hydrocarbon type analysis measured by mass spectrometry using the FI ionization method. More preferably, it is 6% or less.
In the type analysis of hydrocarbons measured by mass spectrometry using the FI ionization method, if the proportion of naphthenobenzenes exceeds 10%, the stability decreases and coking is likely to occur in the nozzle, resulting in long-term operation. Later, the fuel consumption rate decreases and combustion failure tends to occur.

The hydrocarbon type such as naphthenobenzenes referred to in the present invention is obtained by mass spectrometry by the FI ionization method as shown below.
(FIMS analysis conditions)
Device: JMS-AX505H manufactured by JEOL Ltd.
Resolution: 500
Mass number measurement range: m / z 40-500
Sample introduction: Glass reservoir (300 ° C)
Accelerating voltage: 3.0 kV
Cathode voltage: -6.0 kV
Ion source temperature: 90 ° C
Emitter current: 5 mA

The kerosene sample was subjected to mass spectrometry under the above conditions, and each peak was classified according to the type of C _n H _{2n + z} from the obtained mass spectrum, and each ratio was determined 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 the kerosene of the present invention, the ratio of naphthenobenzenes (bicyclic naphthenobenzenes) having a total number of rings of 3 or more determined by the above method is preferably 0.5% or less, and 0.3% Or less, more preferably 0.2% or less.
The total ratio of naphthenobenzenes having a total number of rings of 3 or more and cycloparaffins having a total number of rings of 3 or more is preferably 1% or less, more preferably 0.8% or less, and 0 More preferably, it is 6% or less.
The ratio of naphthenobenzenes with a total number of rings of 3 or more exceeds 0.5%, or the total ratio of naphthenobenzenes with a total number of rings of 3 or more and cycloparaffins with a total number of rings of 3 or more is 1% In particular, the stability is lowered, and the fuel consumption rate is lowered after the long-term operation, and combustion failure tends to occur.

  The kerosene of the present invention has a ratio of naphthenobenzenes of 10% or less, preferably a ratio of naphthenobenzenes having a total number of rings of 3 or more, in the hydrocarbon type analysis measured by mass spectrometry using the FI ionization method. If the total ratio of naphthenobenzenes and cycloparaffins having a total number of rings of 3 or more is 1% or less, other properties are not particularly limited, but have the properties described below. Preferably it is.

Regarding the distillation properties of the kerosene of the present invention, it is preferable to have the following properties.
The initial boiling point is preferably 140 ° C. or higher, more preferably 143 ° C. or higher, and further preferably 145 ° C. or higher. When the initial boiling point is less than 140 ° C., it is not preferable because there is an influence on safety due to a decrease in flash point. On the other hand, from the viewpoint of maintaining ignition characteristics at low temperatures, the temperature is preferably 175 ° C. or lower, and more preferably 170 ° C. or lower.
The end point is preferably 300 ° C. or lower, and more preferably 290 ° C. or lower. When the end point exceeds 300 ° C., soot is likely to be generated at the time of ignition, and particularly when used in a core-type stove, tar tends to adhere to the core.

The 30 vol% distillation temperature (T30) is preferably 170 ° C or higher, more preferably 175 ° C or higher, and further preferably 180 ° C or higher. When T30 is less than 170 ° C., it is not preferable from the viewpoint of heat generation. On the other hand, from the viewpoint of ignitability at low temperatures, the temperature is preferably 210 ° C or lower, more preferably 205 ° C or lower, and further preferably 200 ° C or lower.
The 50 vol% distillation temperature (T50) is preferably 180 ° C or higher, more preferably 185 ° C or higher, and further preferably 190 ° C or higher. When T50 is less than 180 ° C., the fuel consumption rate tends to be insufficient. On the other hand, from the viewpoint of combustibility, it is preferably 230 ° C. or lower, and more preferably 225 ° C. or lower.

The 70 vol% distillation temperature (T70) is preferably 190 ° C or higher, more preferably 195 ° C or higher, from the viewpoint of the amount of heat generated. On the other hand, from the viewpoint of combustibility, it is preferably 250 ° C. or lower, and more preferably 245 ° C. or lower.
The 95% by volume distillation temperature (T95) is preferably 270 ° C. or lower, more preferably 268 ° C. or lower, from the viewpoint of combustibility.
Here, the initial boiling point, T30, T50, T70, T95, and end point mean values measured by JIS K2254 “Petroleum products—distillation test method—atmospheric pressure distillation test method”, respectively.

  The flash point of the kerosene of the present invention is preferably 40 ° C. or higher, and more preferably 41 ° C. or higher. When the flash point is less than 40 ° C., it is not preferable from the viewpoint of handling safety. Note that the flash point here means a value measured by a closed tag type of JIS K2265 “Crude oil and petroleum products—flash point test method”.

  The sulfur content of the kerosene of the present invention is preferably 10 ppm by mass or less, more preferably 5 ppm by mass or less, and further preferably 1 ppm by mass or less. As the sulfur content increases, the odor tends to become stronger. In addition, the sulfur oxides in the combustion exhaust gas are suppressed, and the life of the exhaust gas aftertreatment catalyst installed in the heating equipment is prolonged. It is preferable not to exceed 10 ppm by mass. In addition, the sulfur content as used in the field of this invention means the value measured by JISK2541 "Sulfur content test method".

The aromatic content of the kerosene of the present invention is preferably 25% by volume or less, and more preferably 20% by volume or less from the viewpoint of combustibility. In addition, aromatic content here means content of the total aromatic content measured by Petroleum Institute method JPI-5S-49-97 "petroleum product-hydrocarbon type test method-high performance liquid chromatograph". .
Of the aromatic components, the aromatic components having two or more rings are preferably 1.5% by volume or less, more preferably 1.0% by volume or less, and 0.5% by volume or less. More preferably it is. When the aromatic content of two or more rings exceeds 1.5% by volume, combustibility is lowered and storage stability is lowered.
In addition, the aromatic component more than two rings here means the bicyclic aromatic component measured by Petroleum Institute method JPI-5S-49-97 "petroleum product-hydrocarbon type test method-high performance liquid chromatograph" and Means the sum of the aromatic content of three or more rings.

Density at 15 ℃ of kerosene present invention, 770 kg / ^{m 3} or more, preferably 820 kg / ^{m 3} or less, 780 kg / ^{m 3} or more, more preferably 810Kg / ^{m 3} or less. When the density at 15 ° C. is less than 770 Kg / m ³ , it is not preferable from the viewpoint of fuel consumption rate, and when it exceeds 820 Kg / m ³ , it is not preferable from the viewpoint of combustibility. Here, the density at 15 ° C. means a value measured according to JIS K2249 “Crude oil and petroleum products—density test method and density / mass / capacity conversion table”.

The kinematic viscosity of the kerosene of the present invention at 30 ° C. is preferably 1.0 mm ² / s or more and 1.7 mm ² / s or less, and is 1.1 mm ² / s or more and 1.6 mm ² / s or less. It is more preferable. 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 standpoint of preventing exudation from the core due to residual heat after the stove is extinguished. Here, the kinematic viscosity at 30 ° C. means a value measured by JIS K2283 “Crude oil and petroleum products—Kinematic viscosity test method”.

  The smoke point of the kerosene of the present invention is preferably 21 mm or more, 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 smoke point here means a value measured by JIS K2537 “Petroleum products—aviation turbine fuel oil and kerosene—smoke point test method”.

  The peroxide value of the kerosene of the present invention is preferably 1 mass ppm or less. When the peroxide value exceeds 1 mass ppm, there is a concern about poor combustion due to the generation of peroxide. The peroxide value referred to here means a value measured by the Petroleum Institute method JPI-5S-46-96 “Test method for peroxide value of kerosene”.

  The saturated content of the kerosene of the present invention is preferably 68% by volume or more, more preferably 72% by volume or more, and further preferably 75% by volume or more from the viewpoint of combustibility. In addition, saturated content here means content of the saturated hydrocarbon measured by Petroleum Institute method JPI-5S-49-97 "petroleum product-hydrocarbon type test method-high performance liquid chromatograph".

  From the viewpoint of storage stability, the olefin content of the kerosene of the present invention is preferably 5% by volume or less, more preferably 3% by volume or less, and still more preferably 1% by volume or less. The olefin content here means the content of olefinic hydrocarbons measured by the Petroleum Institute method JPI-5S-49-97 “Petroleum products—Hydrocarbon type test method—High performance liquid chromatograph”.

  The Saybolt color of the kerosene of the present invention is preferably +25 or more in consideration of safety effects such as impurity identification. The Saybolt color here means a value measured by the Saybolt color test method in JIS K2580 “Petroleum products-color test method”.

  The copper plate corrosion (50 ° C., 3 h) of the kerosene of the present invention is preferably 1 or less, and more preferably 1a. When the copper plate corrosion exceeds 1, the metal member may be corroded, which is not preferable. In addition, copper plate corrosion here means the value measured based on JISK2513 "Petroleum product-copper plate corrosion test method" (test temperature 50 degreeC, test time 3 hours).

  The kerosene of the present invention having the above properties has improved stability, odor reduction, flammability, combustibility, safety, and suitability for heating equipment in a well-balanced manner, and makes heating equipment stable over a long period of time. It is possible to drive. Therefore, the kerosene of the present invention is very useful as a heating kerosene used in heating equipment such as an oil stove (for example, a core-type stove) and an oil fan heater.

  Examples of the kerosene base material used in the kerosene of the present invention include hydrodesulfurized kerosene obtained by hydrorefining straight run kerosene obtained from a crude oil atmospheric distillation apparatus, and straight run weight obtained from an atmospheric distillation apparatus. Hydrocracked kerosene obtained by hydrorefining a vacuum gas oil fraction obtained by treating a crude oil or residual oil with a vacuum distillation unit, hydrocracked kerosene obtained by hydrocracking a vacuum gas oil fraction, vacuum gas oil fraction Catalytic cracked kerosene obtained by catalytic cracking of fraction or desulfurized heavy oil, thermal cracked kerosene obtained by pyrolyzing straight-run heavy oil, hydrodesulfurized kerosene obtained by hydrorefining pyrolyzed kerosene, residual oil Ultra-low sulfur kerosene, straight-run kerosene obtained by hydrotreating hydrodesulfurized kerosene, straight-run kerosene and / or hydrorefined kerosene obtained by hydrorefining in the presence of a hydrogenation catalyst in the presence of a hydrogenation catalyst By extraction of hydrodesulfurized kerosene or hydrorefined kerosene Gasoline fraction of GTL (Gas to Liquids) obtained by FT (Fischer-Tropsch) synthesis after decomposing natural gas etc. into carbon monoxide and hydrogen after removing the normal paraffin content And / or a substrate such as a hydrocracked product thereof.

The hydrorefining conditions in the production of the kerosene base material are not particularly limited as long as kerosene having predetermined properties can be obtained, but in the presence of a hydrogenation catalyst, the reaction temperature is 100 to 350 ° C., the hydrogen pressure is 1 to 10 MPa. , LHSV 0.1 to 10 h ⁻¹ , hydrogen / oil ratio 10 to 500 NL / L are preferable.

The hydrogenation catalyst is not particularly limited, and examples thereof include a hydrogenation active metal supported on a porous carrier. An inorganic oxide is preferably used as the porous carrier. Specific examples of the inorganic oxide include alumina, titania, zirconia, boria, silica, and zeolite. In addition, an inorganic oxide composed of alumina and at least one selected from titania, zirconia, boria, silica and zeolite is also preferably used in the present invention.
The active metal of the catalyst used for the hydrotreatment is preferably at least one metal selected from Group 6 metal and Group 8 metal of the Periodic Table. More preferably, it is at least one selected from Ru, Rd, Ir, Pd, Pt, Ni, Co, Mo and W. The active metal may be a combination of these metals. For example, Pt—Pd, Pt—Rh, Pt—Ru, Ir—Pd, Ir—Rh, Ir—Ru, Pt—Pd—Rh, Pt—Rh— A combination of Ru, Ir—Pd—Rh, Ir—Rh—Ru, Co—Mo, Ni—Mo, Ni—W, or the like can be employed.

The kerosene of 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, based on the total amount of kerosene.
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 kerosene falls within the above-mentioned 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.

<Kerose (1)>
An unrefined oil having a sulfur content of 1600 mass ppm, an initial boiling point of 153 ° C., and T95 = 266 ° C. using a cobalt-molybdenum supported alumina catalyst, a reaction temperature of 310 ° C., a hydrogen partial pressure of 3.6 MPa, LHSV 4.8 h ⁻¹ , hydrogen / Hydrogenation purification was performed under the condition of an oil ratio of 130 NL / L to obtain kerosene (1). The general properties of this kerosene (1) are shown in Table 1.

<Kerose (2)>
An unrefined oil having a sulfur content of 1800 ppm by mass, an initial boiling point of 165 ° C., and T95 = 240 ° C., using a cobalt-molybdenum-supported alumina catalyst, a reaction temperature of 308 ° C., a hydrogen partial pressure of 3.5 MPa, LHSV 3.0 h ⁻¹ , hydrogen / Hydrogenation purification was performed under the condition of an oil ratio of 80 NL / L to obtain kerosene (2). The general properties of this kerosene (2) are shown in Table 1.

<Comparison kerosene (1)>
Unrefined oil containing a large amount of naphthene having a sulfur content of 800 ppm by mass, an initial boiling point of 155 ° C., and T95 = 248 ° C. using a cobalt-molybdenum-supported alumina catalyst, a reaction temperature of 315 ° C., a hydrogen partial pressure of 3.3 MPa, LHSV 2.8 h ⁻¹ and hydrogen / oil ratio was 85 NL / L, and hydrorefining was performed to obtain comparative kerosene (1). The general properties of this comparative kerosene (1) are shown in Table 1.

<Comparison kerosene (2)>
A comparative kerosene (2) was obtained by hydrocracking a vacuum distillation light oil of 340-580 ° C. fraction using a zeolite catalyst at a reaction pressure of 10.5 MPa and a reaction temperature of 410 ° C. The general properties of this comparative kerosene (2) are shown in Table 1.

[Examples 1-2 and Comparative Examples 1-2]
After storing kerosene (1) to (2) and comparative kerosene (1) to (2) in a 43 ° C. constant temperature bath for 2 weeks, the following combustion test was performed. Two-week storage in a 43 ° C. constant temperature bath corresponds to a state where kerosene is stored for several months at room temperature, and kerosene with poor stability is in a state where oxidation deterioration has progressed.

(Fuel test)
As heating equipment for the test, a core up-and-down stove (SX-E261Y manufactured by Corona: open-type oil stove core-type natural ventilation type, with exhaust gas purification device), and an oil fan heater (Blue heater FW-3070E manufactured by Dainichi): open-type A sample oil was charged into a petroleum stove vaporization type forced ventilation type without an exhaust gas purification device, and “ignition → normal operation for 5 hours → fire extinguishing” was set as one cycle, and these steps were repeated 100 cycles (500 hours).

In this fuel test, the fuel consumption rate in the first cycle (hereinafter referred to as “fuel consumption rate 1”) and the fuel consumption rate in the final cycle (hereinafter referred to as “fuel consumption rate 2”) were measured. The difference Δ (fuel consumption rate 1−fuel consumption rate 2) was determined. The obtained results are shown in Table 2.
The fuel consumption rates 1 and 2 shown in Table 2 are both relative values when the fuel consumption rate 1 of Comparative Example 1 is 100. When the fuel consumption rate is 1, it means that the larger the value, the worse the fuel consumption. In addition, when the number of cycles increases, the heating efficiency deteriorates due to adhesion of fixed substances to the combustion part, and therefore the fuel consumption rate 2 is usually smaller than the fuel consumption rate 1. The difference Δ (fuel consumption rate 1−fuel consumption rate 2) is an index of the amount of sticking matter adhering to the combustion part and the THC (Total HydroCarbon) concentration. The smaller the value, the better the combustion (fuel consumption) It is meant to suppress the decrease in rate).

From the results in Table 2, it can be seen that by using the kerosene of Examples 1 and 2 according to the kerosene of the present invention, any decrease in the fuel consumption rate can be suppressed.
On the other hand, in the case of Comparative Examples 1 and 2, as shown in Table 2, the fuel consumption rate significantly decreased after the 500-hour test, and misfire due to poor combustion occurred in the oil fan heater. This result suggests that, when the kerosene of Comparative Examples 1 and 2 is used, a sticking matter is generated in the combustion part as compared with the kerosene of the present invention, and combustion failure is likely to occur.

Claims (3)

Na Futenobenzen such ratio is more than 10%, 95 vol% distillation temperature in the distillation characteristic is from 239.5 to 261.5 ° C., the total number of naphthenobenzenes compound with rings a total of three or more rings is 3 or more the total proportion of cycloparaffins 0.6% or less, kerosene, wherein the sulfur content is 10 ppm by mass or less, and a density at 15 ℃ is less than 770 kg / ^{m 3} or more 810kg / ^{m 3.}   The kerosene according to claim 1, wherein the ratio of naphthenobenzenes having a total number of rings of 3 or more is 0.5% or less. Initial boiling point in distillation characteristics are 140 ° C. or higher, endpoint 300 ° C. or less, is 50 vol% distillation temperature of 180 ° C. or higher 230 ° C. or less, a flash point of 40 ° C. or more on a kinematic viscosity at 3 0 ° C. 1. 0~1.7mm ² / s, the smoke point above 21 mm, kerosene according to claim 1 or 2 peroxide is equal to or less than 1 mass ppm.